Liquid crystalline polymer compositions, process, and products

ABSTRACT

Novel compositions comprising a high concentration of one or more extended chain homopolymer, copolymer, or block polymer and certain polyphosphoric acids are prepared. Such compositions are optically anisotropic (liquid crystalline), capable of exhibiting excellent cohesive strength, and are especially suited to the production of high molecular weight ordered polymer fibers by dry-jet wet spinning. These liquid crystalline compositions are capable of being drawn through long air gap distances and spun at exceptionally high spin draw ratios. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

BACKGROUND OF INVENTION

1. Origin of Invention

This invention was made with Government support under U.S. Department ofDefense contract Nos. F33615-81-K-5070, F49620-81-K-0003, and/orF33615-82-C-5079 awarded by the United States Air Force. The Governmenthas certain rights in this invention.

This application is a continuation-in-part of Ser. No. 06/433,831, filedas PCT US82/01285 Sept. 17, 1982, published as WO84/01160 Mar. 29, 1984,§102(e) date Sept. 17, 1982.

2. Technical Field of Invention

The present invention relates broadly to novel anisotropic(liquid-crystalline) extended chain polymerpolyphosphoric acidcompositions, to the production of high molecular weight extended chainpolymers by polycondensation of selected monomers in certainpolyphosphoric acids, and especially to the production of highlyconcentrated polymer compositions from which industrially usefulpolymeric articles such as fibers and films are readily produced.

Among some of the most serious difficulties encountered in theproduction of thermally stable articles such as fibers and films fromextended chain polymers are described in the Background Art below.

3. Reference to Related Applications

Reference is made to another United States patent application filedconcurrently with the present application, both being assigned to SRIInternational and having as one of their inventors, James F. Wolfe. Saidother application is entitled: "Liquid CrystallinePoly(2,6-benzothiazole) Compositions, Process, and Products" and isherein incorporated by reference.

4. Background Art

In general, the class of aromatic heterocyclic extended chain polymersare well known for their outstanding thermal, physical, and chemicalproperties. Unfortunately, these polymers are essentially non-meltingand have proven very difficult to economically process into articles. Inorder to fashion such polymers into desired articles of commerce, forexample fibers, films, fibrids, and the like, it is necessary that theybe in solution or dope form. Although such polymers can be dissolved invarious acidic solvents, such as sulfuric acid, methanesulfonic acid,chlorosulfonic acid, polyphosphoric acid, and the like, difficulty isoften experienced in preparing and using the polymer-acid compositionsor dopes because of poor polymer-acid solubility.

Normally, a precipitated or dried particulate form of the polymer isdissolved in a strong acidic solvent by mixing the (isolated) polymerparticles at elevated temperatures and/or under high pressures for aperiod from several hours to several days. If the polymer is insolublein the particular solvent, other solvents or various solvent mixturesare employed. Usually, heating and cooling cycles are applied andrepeated to obtain a useful dope.

The resulting dopes often contain undissolved polymer and must befiltered before further processing into articles.

Although spinning dopes of polybenzobisoxazole, polybenzimidazole andpolybenzobisthiazole in sulfuric acid and/or methanesulfonic acid and/orchlorosulfonic acid with polymer concentrations above about 10 percentare known in the art, the intrinsic viscosity of these polymers is forthe most part below 5dL/g and oftentimes less than 3dL/g. The cohesivestrength of such dopes is inherently weak and economically lessdesirable for use in dry-jet wet spinning. In the case ofpolybenzobisoxazole, numerous attempts of dry-jet wet spinning anapproximately 10% polybenzobisoxazole/methane sulfonic acid-dope intofibers were not successful (E. W. Choe, et al., in Macromolecules 1981,14, pp. 920-924).

In the case of polybenzimidazole, prior art dopes of this polymer lackadequate strength to maintain filament integrity while dropping throughthe air-gap. In order to overcome this problem U.S. Pat. No. 4,263,245teaches dissolving a high concentration (up to 30%) of this polymer intosuitable solvents such as concentrated sulfuric acid. At such highpolymer concentrations lithium chloride is required to prevent thepolybenzimidazole from phasing out of solution.

In the case of polybenzobisthiazole, U.S. Pat. No. 4,225,700 teaches theformation of a liquid crystalline composition of this polymer atconcentrations near 10% in methane sulfonic acid and chlorosulfonic acidand at about 6% in polyphosphoric acid. Concentrations ofpolybenzobisthiazole in polyphosphoric acid above about 10% by weightare difficult, if indeed possible to achieve. One difficulty encounteredis that the solution of the 2,5-diamino-1,4-benzenedithiol monomer inpolyphosphoric acid with the P₂ O₅ content described in U.S. Pat. No.4,225,700 is very viscous and dehydrohalogenation is difficult. Alsoconsiderable foaming results. Although solutions of precipitated polymerin solvents such as methane sulfonic acid and chlorosulfonic acid can beprepared, high concentrations of polymer are difficult or impossible toachieve. S. R. Allen, et al., in Macromolecules 1981, 14, pp. 1135-1139describes attempts at spinning polybenzobisthiazole directly from thepolymerization medium (polyphosphoric acid) containing 5-6% polymer.

Insofar as polybenzobisthiazole is concerned it is possible to obtaincompositions near to 10% of the polymer in polyphosphoric acid withintrinsic viscosity equal to 26dL/g (J. F. Wolfe, et al., Macromolecules1981, 14, pp. 915-920). Attempts to increase the intrinsic viscosity ofthe polymer can only be achieved at a major sacrifice (decrease) inpolymer concentration. Liquid crystalline compositions of 10%polybenzobisthiazole in polyphosphoric acid are heretofore unknown inthe art. Liquid crystalline compositions of polybenzobisthiazole havingintrinsic viscosities greater than about 30.3dL/g in polyphosphoric acidare heretofore unknown in the art.

In practical terms this means that such polymerpolyphosphoric acidcompositions are severely limited in their potential usefulness for theproduction of highly ordered high molecular weight polymeric articles.

In general, liquid crystalline extended chain polymer compositions (withthe exception of polybenzobisthiazole as mentioned above) inpolyphosphoric acid are heretofore unknown in the art; and moreover,liquid crystalline extended chain copolymer and block polymercompositions are heretofore unknown in the art.

DISCLOSURE OF INVENTION

1. Objects of Invention

Accordingly, it is an object of the present invention to providecompositions substantially free of one or more of the disadvantages ofprior art compositions.

Another object is to provide a process for preparing liquid crystallineextended chain polymer compositions.

A further object is to provide liquid crystalline extended chain polymercompositions having excellent cohesive strength.

Another object is to provide liquid crystalline extended chain polymercompositions having excellent spin stretchability.

Another object is to provide liquid crystalline extended chain polymercompositions capable of being drawn through long air gap distances.

Yet another object is to provide liquid crystalline extended chainpolymer compositions capable of being drawn at high spin draw ratios.

A further object of the invention is to prepare a liquid crystallinespinning composition having a high extended chain polymer content.

A still further object is to provide liquid crystalline extended chainhomopolymer compositions.

Another object is to provide liquid crystalline extended chain copolymercompositions.

Yet another object is to provide liquid crystalline extended chain blockpolymer compositions.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain homopolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain copolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain block polymer.

Another object of the invention is to provide a method of preparingliquid crystalline extended chain polymer compositions from selectedmonomers.

Another object is to provide a process for preparing liquid crystallinehigh molecular weight extended chain polymer compositions.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain homopolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain copolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain block polymers.

A still further object is to provide a method whereby thedehydrohalogenation of certain hydrohalide monomers may be carried outmore easily and rapidly.

Yet another object is to provide a method whereby a substantially higherconcentration of monomeric reactants can be employed which results inliquid crystalline extended chain polymer compositions of considerablyhigher polymer concentration than has been possible heretofore.

Another object is to alleviate the foaming problem referred to above.

Another object is to provide articles prepared from liquid crystallineextended chain polymer compositions.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain homopolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain copolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain block polymers.

Another object of the invention is to provide a process for thecontinuous production of extended chain homopolymer, copolymer, andblock polymer articles such as fibers and films starting with selectedmonomers.

The above and other objects of the invention will be apparent from theensuing description and the appended claims.

2. Statement of Invention

In accordance with our discovery, the present invention broadlyencompasses novel polymer compositions which are useful as dopes in theproduction of high strength shaped articles comprising blends of certainpolyphosphoric acids, as described hereinafter, and a high concentrationof one or more high molecular weight extended chain polymers having oneor more mesogenic group or groups. The extended chain polymers can behomopolymers, copolymers, or block polymers, as exemplified hereinafter.The extended chain polymer is present in the blend at a sufficientconcentration so as to be capable of exhibiting an anisotropic polymerphase alone or in combination with one or more different polymers withor without mesogenic group or groups. The blends according to theinvention are polycondensation products obtained by reaction of selectedmonomers in an appropriate solution of phosphoric acid, as describedhereinafter. These blends exhibit special properties which make themvery useful as dopes in the production of fibers, films, fibrids, andthe like. In addition to being anisotropic (liquid-crystalline), theblends have a novel combination of properties including unexpectedlyhigh spin-stretchability and excellent cohesive strength, as well ashaving the capability of being drawn through short, as well as extremelylong, air-gap distances, and spun at low, as well as exceptionally high,draw ratios. It is believed that these properties can be attributed tothe combination of high polymer concentration, high polymer molecularweight, and a high phosphorus pentoxide content comprising the blends ofthe present invention.

Our discovery further broadly encompasses a process for preparing novelextended chain polymer compositions which are useful as dopes in theproduction of fibers and films. This process comprises:

(a) mixing at least one of a selected first monomer (as describedhereinafter) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a first mixture of the first monomer in the preliminarysolvent,

(c) adding at least one of a selected second monomer (as describedhereinafter) in the resulting mixture of step (b) to provide a firstmixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (c) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(e) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product or a first cooligomeric product having apreselected intrinsic viscosity, or

(f) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomopolymeric product or a first copolymeric product,

(g) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, the secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1g) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (1g) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(3g) causing polymerization of the first or first and second monomer ata temperature sufficient to effect reaction at a rate to form the secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomers ofstep (a) or (1g) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomers of step (a) or (c)which forms the first homo-oligomeric product, or

(h) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of at least one of a selected firstmonomers or a first and second monomer in the preliminary solvent so asto form a monomer-oligomer mixture, and then increasing the phosphoruspentoxide content of the monomer-oligomer mixture to provide amonomer-oligomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization, the first monomer of the second mixturebeing formed by like steps (a) and (b) and the first and second monomerof the second mixture being formed by like steps (a), (b) and (c), withthe overall proviso that at least one of the selected monomers of step(a) or (c) which forms the first or first and second monomer of thesecond mixture, be different from at least one of the selected monomersof step (a) or (c) which forms the first homo-oligomeric product.

(i) causing polymerization of the polyoligomeric product resulting fromstep (g) or the monomer-oligomer resulting from step (h) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

(j) spinning, drawing, extruding, or casting an article from said firsthomo-oligomeric product, said first co-oligomeric product, said firsthomopolymeric product, said first copolymeric product, said firstpoly-oligomeric product, said second homo-oligomeric product, said firstblock-oligomeric product, said first block-polymeric product, ormixtures thereof.

2.a FIGURES

The invention will be more fully explained with reference to the Figureswherein:

FIG. 1. graphically illustrates the weight stability of as spun polymerfibers of --BI]_(n) (Example 13) and --AI]_(n) (Example 12) with timeduring isothermal aging in circulating air at 371° C;

FIG. 2. graphically illustrates the weight stability of precipitatedpolymers of --V]hd n (Example 120) and --T]_(n) (Example 27) with timeduring isothermal aging in circulating air at 371° C.

FIG. 2a. graphically illustrates the weight stability by TGA of blockcopolymers AI--AN" (Example 74) and AI--AG" (Example 73) withtemperature in air at a heating rate of 5° C. per minute;

FIG. 3. graphically illustrates the weight stability by TGA of polymers--T]_(n) (Example 27) and --V]_(n) (Example 120) with temperature inhelium at a heating rate of 5° C. per minute;

FIG. 4. graphically illustrates the weight stability by TGA of polymers--BI]_(n) (Example 13) and --AI]_(n) (Example 12) with temperature inhelium at a heating rate of 5° C. per minute;

FIG. 5. graphically illustrates the weight stability by TGA of polymers--T]_(n) (Example 27) and --V]_(n) (Example 120) with temperature in airat a heating rate of 5° C. per minute;

FIG. 6. graphically illustrates the weight stability by TGA of polymers--BI]_(n) (Example 13) and --AI]_(n) (Example 12) with temperature inair at a heating rate of 5° C. per minute;

FIG. 7. graphically illustrates the relationship of amount of useablePPA and % P₂ O₅ content required to achieve f of 0.822 for selectedpolymer concentrations P_(c) (plot of equation a*) showing a region(shaded dash area) of poor solubility for monomer 1a;

FIG. 8. graphically illustrates the % P₂ O₅ content profile for a 14.8wt % --AI]_(n) polymerization (Example 2) showing the limits ofachievable molecular weight when starting with a high P₂ O₅ contentpreliminary solvent;

FIG. 9. graphically illustrates the % P₂ O₅ content profile for a 8.6 wt% --T]_(n) polymerization (Example 3) showing the limits of achievabledegree of polymerization when starting with a high P₂ O₅ contentpreliminary solvent;

FIG. 10. graphically illustrates a typical % P₂ O₅ content profile for a14.5 wt % --AI]_(n) polymerization (Example 12) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent followed by an increase of P₂ O₅ content at the start ofpolymerization;

FIG. 11. graphically illustrates a typical % P₂ O₅ content profile for a13.0 wt % --BI]_(n) polymerization (Example 13) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent and step-wise addition of P₂ O₅ followed by an increase of P₂ O₅content at the start of polymerization;

FIG. 12. graphically illustrates a typical % P₂ O₅ content profile for a20.3 wt % --T]_(n) polymerization (Example 27) showing the advantages ofthe invention when starting with a low P₂ O₅ content preliminary solventfollowed by an increase of P₂ O₅ content at the start of polymerization;

FIG. 13. graphically illustrates a typical % P₂ O₅ content profile for a16.87 wt % --V]_(n) polymerization (Example 122) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent followed by an increase of P₂ O₅ content at the start ofpolymerization;

FIG. 14. is a % P₂ O₅ profile diagram giving the profile area bounded atABCDEFGHI of % P₂ O₅ for achieving the advantages of this invention.

3. Mode(s) for Carrying Out the Invention

The extended chain polymers of the compositions of the present inventionare a class of polymers that can obtain a substantial degree of shapeanisotropy in the liquid state due to restricted rotation of bonds inthe polymer backbone and/or appropriate catenation geometry of rigidbackbone segments. The degree of shape anisotropy is generally definedby the axial ratio, ρ/d, where ρ is the persistence length of the chainand d is the diameter of the chain. For extended chain polymers, ρ maybe substantially the same as or greater than the contour length 1 of thepolymer. In the case of a rigid rod polymer, ρ is essentially infiniteand the axial ratio is 1/d.

By the method of the present invention, it is possible to prepare liquidcrystalline compositions of extended chain homopolymers, copolymers, orblock polymers containing 15 percent or more of polymer. As will appear,the invention is applicable to the preparation of liquid crystallineextended chain polymer compositions of lower polymer concentration butthere are special advantages to preparing compositions of highconcentration.

Extended chain polymer-polyphosphoric acid compositions of such higherpolymer concentration are advantageous. For example, if the polymer isone, such as polybenzobisthiazole, polybenzobisoxazole, andpolybenzobisimidazole, capable of forming liquid crystallinecompositions at low concentration (e.g., 5-10%), that is, if thecritical concentration necessary for formation of the anisotropic phaseis low, compositions of even higher polymer concentration can be spun toproduce a better quality, higher strength fiber. We believe thisresults, in part at least, from a more fully anisotropic composition andimproved composition integrity. These improvements allow greater drawingin the air-gap, improve the coagulation characteristics, which leads tofewer flaws, and increase polymer throughput when a liquid crystallinecomposition is spun by a dry-jet-wet spinning technique into apolyphosphoric acid-solvent/polymer-nonsolvent such as methanol, water,or dilute aqueous acid(s).

If the polymer is one, such as poly (2,6-benzothiazole) that is lessrodlike in structure than polybenzobisthiazole or polybenzobisoxazoleand thus possesses a critical concentration for anisotropic phaseformation greater than 10% and in the region of concentrations of thisinvention, extruding of these heretofore unattainable solutions producesa dramatic increase in strength and modulus because of the ordering ofthe polymer during this fabrication.

These advantages result in a more highly ordered, lower-defect fiberthan results from spinning a less concentrated composition of polymers.

Another advantage of preparation of these polymers in the anisotropicphase is a considerable increase in the molecular weight of the polymerobtained.

Preliminarily it is helpful to describe the chemistry of phosphoricacids and strong phosphoric acids or polyphosphoric acids as follows:

As used herein the term "phosphoric acid(s)" means commercial phosphoricacid(s) containing 85-86% H₃ PO₄.

The strong phosphoric acids, or polyphosphoric acids referred to as ppa(polyphosphoric acid) are members of a continuous series of amorphouscondensed phosphoric acid mixtures given by the formula

    H.sub.n+2 P.sub.n O.sub.3n+1

or

    HO--PO.sub.3 H.sub.n H

where the value of n depends on the molar ratio of water to phosphoruspentoxide present.

Characterization and methods of forming various polyphosphoric acids andexamples of such strong acids useful in accordance with the practice ofthe present invention can be found in the following papers: A. L. Huhtiand P. A. Gartaganis "The Composition of the Strong Phosphoric Acids,"Can. J. Chem., Vol. 34, 1956 pp. 785-797; and J. E. Such, "LinearPolyphosphoric Acids", Mellar's Comprehensive Treatise on Inorganic andTheoretical Chemistry, Vol. VIII, Supplement III, pp. 726-753, Wiley1971. The subject matter of these articles are specifically incorporatedherein by reference.

In its most general definition, polyphosphoric acid composition canrange from distributions where the average value of n is less thanunity, giving rise to a mobile liquid, to high values of n, where thepolyphosphoric acid is a glass at normal temperatures. Because thespecies of polyphosphoric acid are in a mobile equilibrium, a givenequilibrium composition can be prepared in many ways. For instance, thesame distribution or polyphosphoric acid composition could be preparedby either starting with concentrated orthophosphoric acid (H₃ PO₄, n=1)and driving off water or by starting with phosphorus pentoxide (P₂ O₅)and adding an appropriate amount of water.

All polyphosphoric acid compositions can be described as a ratio of P₂O₅ and water by reducing the various species present (on paper) to P₂ O₅and water. We will then use the convention that polyphosphoric acidcomposition will be expressed in terms of a P₂ O₅ content (as apercentage) defined as P₂ O₅ content ##EQU1## Thus, the P₂ O₅ content ofpure orthophosphoric acid could be derived by reducing one mole of H₃PO₄ to 0.5 moles P₂ O₅ +1.5 moles H₂ O. Converting to weights gives theP₂ O₅ content as ##EQU2##

Similarly, the P₂ O₅ content of commercial polyphosphoric acid can bederived in the following way. Polyphosphoric acid is availablecommercially in two grades, 105% and 115%. These percentages refer to H₃PO₄ content, which means that 100 g of the two grades contain 105 and115 grams of H₃ PO₄. The P₂ O₅ content of 115% polyphosphoric acid canthen be calculated knowing the P₂ O₅ content of 100% H₃ PO₄. ##EQU3##Freshly prepared polyphosphoric acid as described by Wolfe and Loo U.S.Pat. 4,225,700 employed 1.52×g of P₂ O₅ to ×grams of 85.6% H₃ PO₄, thusthe P₂ O₅ content of that mixture is ##EQU4##

Thus, polyphosphoric acid compositions, by our definition, equivalent tothese three examples could be prepared in principle by starting with P₂O₅ and adding 27.6, 16.7, and 15.1% by weight of water.

Homopolymeric Compositions and their preparation

In accordance with one aspect of the invention, there is provided aliquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain homopolymer having thegeneral formulas: ##STR1## wherein Ar¹ represents an aromatic moiety andis XX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or represents a bivalent organic radical and isXXI as defined below, n being a positive integer; ##STR2## wherein Ar³represents an aromatic moiety and is XXII as defined below, X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₃ being bonded to aromatic carbon atoms of Ar³, Nand X₃ of each hetero ring are disposed ortho to one another, n being apositive integer; ##STR3## wherein Ar¹ represents an aromatic moiety andis XX as defined below, and Ar⁴ represents an aromatic moiety and isXXIII as defined below, the nitrogen atoms being bonded to aromaticcarbon atoms of Ar¹ and the carbon atoms being bonded to aromatic carbonatoms of Ar⁴, n being a positive integer; ##STR4## wherein Ar⁵represents an aromatic moiety and is XXIV as defined below, the nitrogenatoms being bonded to Ar⁵, n being a positive integer; ##STR5## whereinAr⁶ represents an aromatic moiety and is XXV as defined below, Ar¹represents a different aromatic moiety and is XX as defined below, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, n being a positive integer;##STR6## wherein Ar⁹ represents an aromatic moiety and is XXVI asdefined below, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁹, n being a positive integer; ##STR7## wherein Ar¹represents an aromatic moiety and is XXVII as defined below, Y⁷represents an aromatic moiety and is XXVIII as defined below, thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer; ##STR8##wherein Ar¹ represents an aromtic moiety and is XX as defined below, Y⁸is XXIX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹ and adjacent carbon atoms of Y⁸, N and X₁ or X₂ of each hetero ringare disposed ortho to one another, n being a positive integer.

The aromatic moieties Ar¹, Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁹, and Y², Y⁷, and Y⁸of the extended chain polymer formulas above are defined as follows:##STR9## Any monomeric material or mixture of monomeric materials havingthe ability to react in polyphosphoric acid to form the extended chainpolymers (i.e., the above formulas I-VIII homopolymers, and the variousformulas IX-XIX copolymers and block polymers herein defined in thespecification) of this invention can be utilized.

In general, suitable monomeric materials selected for use in formingliquid-crystalline extended chain polymer compositions of the presentinvention are of nine types as described below. Type 1, 2, 4, 6, 7, and8 are homo-bifunctional monomers. Type 3, 5, and 9 arehetero-bifunctional monomers.

Type 1 monomers have the general formula ##STR10## wherein Ar¹ is anaromatic moiety; X₁ and X₂ are the same or different atoms or groupsselected from the class O, S, and NR; R is hydrogen or an organic groupattached to N; the R's on the two nitrogen atoms where both X₁ and X₂are NR may be the same or different; NH₂, X₁ H and X₂ H are bonded toaromatic carbon atoms of Ar¹ ; the groups on the left side of Ar¹ areortho with respect to one another and the groups on the right side ofAr¹ are ortho with respect to one another.

The two sets of NH₂ and XH are positioned on Ar¹ such that they do notboth interact partially with the appropriate condensing moiety ofanother monomer. Monomer 1 is typically isolated as a hydrohalide saltof the monomer.

In general, Ar¹ may be any aromatic moiety (carbocyclic or heterocyclic)and it may be a single ring such as ##STR11## or it may comprise aplurality of aromatic rings connected by valence bonds or by linkingatoms or groups such as ##STR12## where β is a valence bond (as indiphenyl) or a divalent atom (--O-- or --S--) or group such as--NR--(R=H or an organic group), --(CH₂)_(n) -- (n=1 or a higherinteger). Specific examples of Ar¹ are as follows: ##STR13## Thearomatic ring or rings of Ar¹, such as those described above and others,may bear one or more substituent. These substituents, which may beorganic or inorganic may be or may contain hetero atoms, may be any atomor group which is compatible with the reactant, the solvent, thepolycondensation reaction and the resulting oligomer or polymer.Substituents which are chemically reactive with types 2 thru 9 monomers(see below), with the solvent (PPA) or with the oligomeric or polymericproducts are to be avoided. Also, substituents which offer sterichindrance to the polycondensation are to be avoided.

Among permissible hydrocarbon substituents are alkyl (e.g., C₁ to C₁₀straight chain and branched chain alkyl, benzyl, etc.), phenyl chlorosubstituted alkyl, phenyl and benzyl. Among permissible heterosubstituents are chloro, bromo, nitro, alkoxy, aryloxy, SO₃ H, and --OR,SR, and --NR₁ R₂ (R₁ and R₂ being organic groups).

Formula 1 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (1,1), Class 2 (1,2),and Class 3 (1,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (1,1) monomers are those wherein Ar¹ is a six-memberedaromatic ring with the four valence positions being on carbon atomshaving a 1, 2, 4, 5 relationship to each other, such as 1, 2, 4,5-benzene or 2, 3, 5, 6-pyridine; R is H or a monovalent aromaticradical, such as phenyl, or a monovalent heteroaromatic radical, such as2-pyridyl, or a monovalent aliphatic radical, such as methyl. Monomers(1,1) which when reacted with a diacid or a diacid derivative give twosubstantially collinear bonds are most preferred.

Specific examples of (1,1) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 1 below.

                  TABLE 1                                                         ______________________________________                                        Monomers of Type 1, Class 1                                                   ______________________________________                                         ##STR14##                                                                    2,5-diamino-1,4-benzenedithiol dihydrochloride                                obtained according to Wolfe, et. al.,                                         Macromolecules, Vol. 14, Page 915 (1981).                                      ##STR15##                                                                    4,6-diamino-1,3-benzenediol dihydrochloride                                   obtained from 4,6-dinitro-1,3-benzenediol                                     according to Wolfe, et al., Macromolecules, Vol.                              14, Page 909 (1981).                                                           ##STR16##                                                                    1,2,4,5-tetraaminobenzene tetrahydrochloride                                  obtained from Aldrich Chemical Co. and purified                               by recrystallization from dilute HCl by heating,                              adding charcoal, filtering, and adding                                        concentrated HCl.                                                              ##STR17##                                                                    2,5-diamino-1,4-benzenediol dihydrochloride                                   prepared according to Wolf, et. al., J. Polymer                               Sci., Part A-1, Vol. 6, page 1503 (1968).                                      ##STR18##                                                                    2,3,5,6-tetraaminopyridine trihydrochloride                                   prepared by the dinitration of 2,6-diamino                                    pyridine, followed by hydrolysis and reduction by                             the method of A. H. Gerber, J. Polymer Sci.,                                  Polymer Chemistry Ed., Vol. 11, page 1703(1973).                               ##STR19##                                                                    3,5-diamino-2,6-pyridinediol trihydrochloride                                 prepared by dinitration of 2,6-dimethoxy pyridine                             according to C. D. Johnson, et al., J. Chem. Soc.                             (B), 1967, page 1204, followed by reduction and                               dealkylation.                                                                  ##STR20##                                                                    3,6-diamino-2,5-pyridinedithiol dihydrochloride                               prepared from commercially available 2,5-                                     diamino-pyridine by methods analogous to the                                  preparation of 1a.                                                             ##STR21##                                                                    N.sup.1,N.sup.5diphenyl-1,2,4,5-tetraaminobenzene dihydrochloride             prepared starting from m-dichlorobenzene                                      according to H. Vogel and C. S. Marvel, J.                                    Polym. Sci., A, Vol. 1, page 1531 (1963) and                                  purified from toluene before use.                                             ______________________________________                                    

The preferred (1.2) monomers are those wherein Ar¹ is two six-memberedaromatic rings attached by a covalent carbon-carbon bond each withvalences on carbon atoms in the 3 to 4 positions, such as3,3',4,4'-biphenyl or 4,4', 5,5'-(2,2'-bipyridyl), or Ar¹ is two fusedsix-membered rings with valence positions being on carbon atoms andhaving a 1,2,5,6 relationship to each other, such as1,2,5,6-naphthalene.

The four functional groups attached to the valence positions of Ar¹ bycovalent bonds comprise two amino groups and the groups --X₁ H and --X₂H such that one amino group is ortho to --X₁ H and the other amino groupis ortho to X₂ H and X₁ H is attached to either the 3 or 4 position inthe first case or the 1 or 2 position in the second case and --X₂ H isattached to either the 3' or 4' position in the first case and the 5 or6 position in the second case. X₁ and X₂ are defined as above.

Specific examples of (1,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Monomers of Type 1, Class 2                                                   ______________________________________                                         ##STR22##                                                                    1i                                                                            3,3'-dimercaptobenzidine dihydrochloride                                      prepared by the method of Houben-Weyl, Methoden                               der Organischen Chemie, E. Miller, Ed., Vol IX, page 39 (1955).                ##STR23##                                                                    1j                                                                            3,3'-dihydroxybenzidine dihydrochloride                                       prepared by the method of C. G. Vogt and F.                                   Marschall, U.S. Pat. No. 2,497,248 (1950) from                                o-dianisidine and aluminum chloride.                                           ##STR24##                                                                    1k                                                                            3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride                           prepared by the method of Y. Imai, I. Taoka, K.                               Uno, and Y. Iwakura, Makromol. Chem, 83, page 167 (1965).                      ##STR25##                                                                    1l                                                                            3,3'-diaminobenzidine tetrahydrochloride dihydrate                            prepared according to (same ref. as for 1h) and                               the tetrahydrochloride recrystallized from dilute                             HCl containing stannous chloride by adding                                    concentrated HCl.                                                              ##STR26##                                                                    1m                                                                            3,3'-diamino-4,4'-dianilinobiphenyl dihydrochloride                           prepared from dinitration of 4,4'-                                            dichlorobiphenyl, displacement of the chloro                                  groups by aniline, and reduction.                                              ##STR27##                                                                    1n                                                                            1,5-diamino-2,6-naphthalenedithiol dihydrochloride                            by methods analogous to Monomers 1a and 1i.                                    ##STR28##                                                                    1o                                                                            1,5-diamino-2,6-naphthalenediol dihydrochloride                               prepared from 2,6-dichloro-1,5-dinitro-naphthalene.                            ##STR29##                                                                    1p                                                                            1,2,5,6-tetraminonaphthalene tetrahydrochloride                               prepared by the amination of 2,6-dichloro-1,5-                                dinitro-naphthalene followed by catalytic                                     reduction according to K. Imai, N. Kurihara, L.                               Mathias, J. Wittmann, W. B. Alston, and J. K.                                 Stille, Macromolecules, 6, 158 (1973).                                        ______________________________________                                    

The preferred (1,3) monomers are those wherein Ar¹ is any aromaticmoiety with two sets of ortho-valences at carbon atoms, such as##STR30## wherein β is a bivalent aromatic or heteroaromatic moiety, O,S, SO₂, C═O, --CH₂ CH₂ --, etc.

The four functional groups attached to the valence positions of Ar¹ aredivided into two sets (NH₂ and X₁ H) and (NH₂ and X₂ H) with thefunctional groups within each set being positioned ortho to each otherand the two sets positioned on Ar¹ such that they cannot simultaneouslyreact with the same functional group of another monomer. X₁ and X₂ aredefined as above.

Specific examples of (1,3) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 3below.

                  TABLE 3                                                         ______________________________________                                        Monomers of Type 1, Class 3                                                   ______________________________________                                         ##STR31##                                                                    1q                                                                            3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride                    prepared according to the method of V. V.                                     Korshak, E. S. Krongauz, A. P. Travnikova, A. L.                              Rasanov, and A. D. Katsarava, Dokl, Akad. Nauk.                               SSSR, 196, 106 (1971).                                                         ##STR32##                                                                    1r                                                                            3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride                         obtained commercially from Pfaltz & Bauer.                                     ##STR33##                                                                    1s                                                                            3,3'-dihydroxy-4,4'-diaminodiphenyl ether                                     is prepared according to the method of S. U.                                  Kantor and J. Sonnenberg, U.S. Pat. No. 3,306,876                             (1967).                                                                        ##STR34##                                                                    1t                                                                            3,3'-diamino-4,4'-dihydroxydiphenyl ether                                     prepared according to the method of A. S.                                     Lindsey, S. E. Hunt, and G. K. L. Gibson, U.K.                                Patent No. 1,181,531 (1970).                                                   ##STR35##                                                                    1u                                                                            3,3',4,4'-tetraaminodiphenyl sulfone                                          prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by acetylation,                                       dinitration, hydrolysis, and reduction.                                        ##STR36##                                                                    1v                                                                            3,3'-dimercapto-4,4'-diaminodiphenyl sulfone                                  prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by methods analogous to                               the preparation of 1a and 1i.                                                  ##STR37##                                                                    1w                                                                            3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone                                   prepared according to the method of G. I. Braz,                               I. Y. Kardash, and V. S. Yakubovich, Polym. Sci.                              USSR., 8, page 2013 (1967).                                                    ##STR38##                                                                    1x                                                                            3,3'-diamino-4,4'-dihydroxydiphenyl sulfone                                   prepared from commercially available 4,4'-                                    dihydroxydiphenyl sulfone by acetylation,                                     dinitration, hydrolysis and reduction.                                         ##STR39##                                                                    1y                                                                            3,3',4,4'-tetraaminobenzophenone                                              available commercially from Polysciences, Inc.                                 ##STR40##                                                                    1z                                                                            3,6-diamino-1,2-benzenedithiol dihydrochloride                                prepared by isolation of 2,7-diaminobenzo[1,2-                                d;6,5-d']bisthiazole from the scheme to prepare                               1a followed by hydrolysis.                                                    ______________________________________                                    

Type 2 monomers has the general formula

    Z.sub.1 --Y.sup.2 --Z.sub.2                                2

wherein Y² is a bivalent organic group and Z₁ and Z₂ areelectron-deficient carbon groups and may be the same or different groupsselected from the followingclass:______________________________________--COOH --CSSH --COBr--CSI--CSOH --COCl --CSBr --CONHR₁--COSH --CSCl --COI --CSNHR₁--CN______________________________________

(R₁ =H or an organic group bonded to N by a carbon atom)

The only requirement of Z₁ and Z₂ is that they react with the X₁ H andX₂ H and with the two hydrogen atoms of the primary amino groups of Type1 monomers to form suitable leaving entities, such as water, hydrogensulfide, hydrogen halide, ammonia, etc.

The bivalent group Y² may be an aromatic group, an acyclic aliphaticgroup, or a cycloaliphatic group, and such groups may be substituted byhydrocarbon groups (aliphatic or aromatic) and by hetero atoms andgroups. In general any of groups described above as substituents of thearomatic ring or rings of Ar¹ may be used subject to the samerestrictions.

Formula 2 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (2,1), Class 2 (2,2),and Class 3 (2,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (2,1) monomers are those wherein Y² is nil, or Y₂ compriseat least two carbon atoms to which are attached Z₁ and Z₂ such that thetwo exocyclic bonds between Y² and Z₁ and between Y² and Z₂ have a rigidand fixed relationship to each other and are substantially collinear, orY² may also be a cycloaliphatic group that has at least two carbon atomsto which are attached Z₁ and Z₂ such that the two bonds between Y² andZ₁ and between Y² and Z₂ have a highly preferred relationship to eachother that is substantially collinear. Carboxylic acid derivatives of2j-2q and 2z (as herein described below) such as COOH that decarboxylateat temperatures below that required for polycondensation with Type 1monomers are less preferred.

Specific examples of (2,1) monomers preferred for use in the inventioninclude those monomers in Table 4 below.

                  TABLE 4                                                         ______________________________________                                        Monomers of Type 2, Class 1                                                   ______________________________________                                         ##STR41##                                                                    2a                                                                            terephthalic acid                                                             obtained from Amoco Chemicals Co. and micronized                              and dried before use.                                                          ##STR42##                                                                    2b                                                                            terephthaloyl chloride                                                        obtained from Aldrich and sublimed immediately                                before use.                                                                    ##STR43##                                                                    2c                                                                            1,4-benzenedicarboxamide                                                      prepared from 2b or obtained commercially from                                Pfaltz and Bauer.                                                              ##STR44##                                                                    2d                                                                            terephthalonitrile                                                            obtained from Pfaltz and Bauer.                                                ##STR45##                                                                    2e                                                                            trans-1,4-cyclohexanedicarboxylic acid                                        obtained from Aldrich and recrystallized from                                 water.                                                                         ##STR46##                                                                    2f                                                                            trans-1,4-cyclohexanedicarboxylic acid chloride                               prepared from 2e.                                                              ##STR47##                                                                    2g                                                                            trans-1,4-cyclohexanedicarboxamide                                            prepared from 2f.                                                              ##STR48##                                                                    2h                                                                            trans-1,4-dicyanocyclohexane                                                  prepared from 2g.                                                              ##STR49##                                                                    2i                                                                            2,5-pyridinedicarboxylic acid                                                 obtained from Aldrich Chemical Co.                                             ##STR50##                                                                    2j                                                                            2,6-benzo[1,2-d:4,5-d']bisthiazoledinitrile                                   prepared by diazotization of 2,6-                                             diaminobenzobisthiazole (see reference for 1a)                                followed by treatment with cuprous cyanide.                                    ##STR51##                                                                    2k                                                                            2,6-benzo[1,2,-d:5,4-d']bisoxazoledinitrile                                   prepared from the condensation of compound 1b                                 with urea followed by diazotization as for                                    compound 2j.                                                                   ##STR52##                                                                    2l                                                                            2,6-benzobisimidazoledinitrile                                                prepared as for 2k using compound 1c.                                          ##STR53##                                                                    2m                                                                            2,6-benzo[1,2-d:4,5-d']bisoxazoledinitrile                                    prepared as described for 2k using compound 1d.                                ##STR54##                                                                    2n                                                                            2,6-pyridobisimidazoledinitrile                                               prepared as for 2k using compound 1e.                                          ##STR55##                                                                    2o                                                                            2,6-pyrido[2,3-d:6,5-d']bisoxazoledinitrile                                   prepared as for 2k using compound if.                                          ##STR56##                                                                    2p                                                                            2,6-pyrido[2,3-d:5,6-d']bisthiazoledinitrile                                  prepared as for 2j, using 2,6-                                                diaminopyridobisthiazole as prepared                                          in the synthesis of 1g.                                                        ##STR57##                                                                    2q                                                                            1,7-diphenyl-2,6-benzobisimidazoledinitrile                                   prepared as for 2k using compound 1h.                                          ##STR58##                                                                    2r                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisthiazole                        prepared by the condensation of compound 1a with                              p-toluic acid followed by oxidation.                                           ##STR59##                                                                    2s                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:5,4-d']bisoxazole                         prepared by the condensation of 1b with p-toluic                              acid followed by oxidation.                                                    ##STR60##                                                                    2t                                                                            2,6-bis(4-carboxyphenyl)benzobisimidazole                                     prepared by a method similar to 2s using 1c.                                   ##STR61##                                                                    2u                                                                            2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisoxazole                         prepared by method similar to 2s using 1d.                                     ##STR62##                                                                    2v                                                                            2,6-bis(4-carboxyphenyl)pyridobisimidazole                                    prepared by a method similar to 2s using 1e.                                   ##STR63##                                                                    2w                                                                            2,6-bis(4-carboxyphenyl)pyrido[2,3-d:6,5-d']bisoxazole                        prepared by a method similar to 2s using 1f.                                   ##STR64##                                                                    2x                                                                            2,6-bis(4-carboxyphenyl)pyrido[2,3-d:5,6-d']bisthiazole                       prepared by a method similar to 2s using 1g.                                   ##STR65##                                                                    2y                                                                            1,7-diphenyl-2,6-bis(4-carboxyphenyl)benzobisimidazole                        prepared by a method similar to 2s using 1h.                                   ##STR66##                                                                    2z                                                                            oxamide                                                                       obtained from Aldrich Chemical Co.                                            ______________________________________                                    

The preferred (2,2) monomers are those wherein Y² comprise twosix-membered rings attached by a covalent carbon-carbon bond each withvalences on the 4-position or each with valences on the 3-position, suchas 4,4'-biphenyl or 3,3'-biphenyl, or Y² comprise two fused six-memberedrings with valence positions being on carbon atoms and having a 1,5relationship to each other, such as 2,6-naphthalene or 2,6-quinoline, orY² is a cycloaliphatic divalent moiety with valences on carbon atoms andin a 1,2-trans configuration, or Y² is a variety of condensed aromaticand heteroaromatic ring systems attached only by carbon-carbon bonds andhaving 2 valences, Z₁ and Z₂ are the same as defined above.

Specific examples of (2,2) monomers preferred for use in the inventioninclude those monomers in Table 5 below.

                  TABLE 5                                                         ______________________________________                                        Monomers of Type 2, Class 2                                                   ______________________________________                                         ##STR67##                                                                    4,4'-biphenyldicarboxylic acid                                                obtained from Aldrich Chemical Co.                                             ##STR68##                                                                    4,4'-biphenyldicarboxylic acid chloride                                       prepared from 2aa.                                                             ##STR69##                                                                    2,6-naphthalenedicarboxylic acid                                              prepared according to the method of B. Raecke and                             H. Schirp. Org. Syn. Coll. Vol. V. page 813                                   (1973) from commercially available 1,8-                                       naphthalenedicarboxylic anhydride.                                             ##STR70##                                                                    2,6-naphthalenedicarboxylic acid chloride                                     prepared from 2cc by treatment with thionyl chloride.                          ##STR71##                                                                    2,6-quinolinedicarboxylic acid                                                prepared from commercially available (Aldrich)                                2,6-dimethyl quinoline by oxidation.                                           ##STR72##                                                                    3,3' -biphenyldicarboxylic acid                                               prepared from o-nitrobenzoic acid by the method                               of M. Kurihara and N. Yoda. J. Macromol. Sci.                                 Chem A1(6), page 1069 (1967).                                                  ##STR73##                                                                    trans-1,2-cyclohexanedicarboxylic acid                                        was obtained from Aldrich Chemical Co. and                                    recrystallized from methanol before use.                                       ##STR74##                                                                    1,4-bis(5-carboxybenzoxazole-2-yl)benzene                                     prepared by the method of J. Preston, W. De                                   Winter and W. L. Hofferbert, J. Heterocyclic                                  Chem. 5, page 269 (1968).                                                      ##STR75##                                                                    1,4-bis(6-carboxybenzothiazole)-2-yl)benzene                                  prepared by methods analogous to 2hh.                                          ##STR76##                                                                    2,5-bis(6-carboxybenzothiazole-2-yl)pyridine.                                 prepared by methods analogous to 2hh.                                         ______________________________________                                    

The preferred (2,3) monomers are those wherein Y² may be any anionic,heteroaromatic and aliphatic divalent species not previously described.

Specific examples of (2,3) monomers preferred for use in the inventioninclude those monomers in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Monomers of Type 2, Class 3                                                   ______________________________________                                         ##STR77##                                                                    4,4'(p-phenylenedioxy)dibenzoyl chloride                                      prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR78##                                                                    4,4'(p-phenylenedioxy)dibenzonitrile                                          prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20(1), page 179 (1979).                                            ##STR79##                                                                    4,4'-(m-phenylenedioxy)dibenzoic acid                                         prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20(1), page 179 (1979).                                            ##STR80##                                                                    4,4'-(m-phenylenedioxy)dibenzoyl chloride                                     from 2mm according to method of R. C. Evers, F.                               E. Arnold, and T. E. Helminiak, Macromolecules,                               14, page 925 (1981).                                                           ##STR81##                                                                    4,4'-(m-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR82##                                                                    3,3'-(m-phenylenedioxy)dibenzoyl chloride                                     according to the method of R. C. Evers, F. E.                                 Arnold, and T. E. Helminiak Maromolecules, 14,                                page 925 (1981).                                                               ##STR83##                                                                    3,3'-(p-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR84##                                                                    4,4'-(o-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR85##                                                                    isophthalic acid obtained from                                                Pfaltz and Bauer and recrystallized                                           from 90% ethanol.                                                              ##STR86##                                                                    4,4'-dicarboxydiphenyl ether                                                  obtained from Polysciences, Inc.                                               ##STR87##                                                                    3,3'-dicarboxydiphenyl ether                                                  prepared from a coupling of m-cresol and m-                                   bromotoluene followed by oxidation by the method                              of M. Tomita, J. Pharm. Soc., Japan, 57, page                                 391 (1937).                                                                    ##STR88##                                                                    succinic acid obtained                                                        from Aldrich Chemical Co.                                                      ##STR89##                                                                    glutaric acid obtained                                                        from Aldrich Chemical Co.                                                      ##STR90##                                                                    adipic acid obtained                                                          from Aldrich Chemical Co.                                                      ##STR91##                                                                    pimelic acid obtained from                                                    Aldrich Chemical Co.                                                           ##STR92##                                                                    sebacic acid obtained from                                                    Aldrich Chemical Co.                                                          ______________________________________                                    

Type 3 monomers has the general formula ##STR93## wherein Ar³ is atrivalent aromatic or heteroaromatic moiety, and X₃ is O, S, or N-R (R═Hor an organic group).

Formula 3 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into two groups: Class 1 (3,1) and Class 2 (3,2).The first number of the number pairs denotes the monomer type and thesecond number of the pairs denotes the monomer class.

The preferred (3,1) monomers are those wherein Z₃ is the same as definedfor Z₁, Ar³ is a trivalent aromatic or heteroaromatic moiety with thethree valence positions being on carbon atoms and having therelationship that the valence bond between Z₃ and Ar³ is nearlycollinear with the same valence bond in subsequently condensed monomers,and X₃ is defined as for X₁ in Table 1. X₃ and NH₂ are positioned orthoto each other on Ar³.

Specific examples of (3,1) monomers preferred for use in the inventioninclude the monomer in Table 7 below.

                  TABLE 7                                                         ______________________________________                                        Monomers of Type 3, Class 1                                                   ______________________________________                                         ##STR94##                                                                    2-(4-carboxyphenyl)-5,6-diaminobenzimidazole                                  dihydrochloride                                                               prepared according to R. F. Kovar, and F. E.                                  Arnold, J. Polym. Sci. Polym. Chem. Ed., 14, page                             2807 (1976).                                                                  ______________________________________                                    

The preferred (3,2) monomers are those wherein Z₃, Ar³, and X₃ aredefined as above. The bonds that are formed in homopolymerization of(3,2) monomers are defined in their spatial relationship having an angleof catenation of about 150° to about 180°.

Specific examples of (3,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 8below.

                  TABLE 8                                                         ______________________________________                                        Monomers of Type 3, Class 2                                                   ______________________________________                                         ##STR95##                                                                    3-mercapto-4-aminobenzoic acid hydrochloride                                  prepared according to Wolfe, AFOSR Final Technical                            Report, Dec. 15, 1980.                                                         ##STR96##                                                                    3-mercapto-4-aminobenzoic acid                                                prepared as described in Example 5.                                            ##STR97##                                                                    3-hydroxy-4-aminobenzoic acid hydrochloride                                   prepared as described by Y. Imai, K. Uno, and Y.                              Iwakura, Makromol. Chem., 83, 179 (1965).                                      ##STR98##                                                                    3-amino-4-hydroxybenzoic acid hydrochloride                                   prepared as described by K. Auwers and H. Rohrig.                             Chem. Ber., 30, 992 (1897).                                                    ##STR99##                                                                    3,4-diaminobenzoic acid                                                       obtained from Aldrich Chemical Co. and                                        recrystallized from deoxygenated water before                                 use.                                                                           ##STR100##                                                                   N.sup.3phenyl-3,4-diaminobenzoic acid                                         prepared from p-aminobenzoic acid by                                          chlorination, oxidation to 3-chloro-4-                                        nitrobenzoic acid, followed by anilation and                                  reduction.                                                                     ##STR101##                                                                   N.sup.4phenyl-3,4-diaminobenzoic acid                                         prepared by nitration of commercially available                               (Aldrich) p-chlorobenzoic acid, followed by                                   anilation and reduction.                                                       ##STR102##                                                                   4-carboxy-3'-mercapto-4'-aminobiphenyl                                        prepared by nitration of commercially available                               4-carboxybiphenyl (ICN/K and K) and reduction to                              4-amino-4'-carboxybiphenyl, followed by placement                             of the o-mercapto group by methods analogous to                               those described for 3a.                                                        ##STR103##                                                                   4-carboxy-3'-amino-4'-hydroxybiphenyl                                         prepared by the nitration of commercially                                     available (ICN/K and K) 4-carboxybiphenyl,                                    conversion to 4-carboxy-p-phenol by reduction and                             diazotization, followed by acetylation,                                       nitration, hydrolysis, and reduction.                                          ##STR104##                                                                   4-carboxy-3',4'-diaminobiphenyl                                               prepared by acetylation of 4-amino-4'-                                        carboxylbiphenyl (see preparation of 3h) followed                             by nitration, hydrolysis, and reduction.                                      ______________________________________                                    

Type 4 monomers have the general formula ##STR105## wherein Z₄, Z₅, Z₆,and Z₇ are the same or different and are chosen from the list ofcarboxylic acid derivatives given for Z₁ in Table 4. Z₄ and Z₅, or Z₆and Z₇, or both sets can also be carboxylic acid anhydride groups. Ar⁴is an aromatic or aromatic heterocyclic moiety having four valencepositions at carbon atoms. Ar⁴ can be a six-member ring with the valencepositions having 1, 2, 4, 5 relationship, or Ar⁴ can be two condensedsix-member rings, such as naphthalene. Z₄ and Z₅ as one set and Z₆ andZ₇ as another set must either be ortho-positioned within each set orbear a 1, 4, 5, 8 relationship to each other. An (imaginary) lineperpendicular to the bond between the valence carbons attached to Z₄ andZ₅ must be collinear with the corresponding (imaginary) line for Z₆ andZ₇.

Formula 4 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (4,1). The first number of the number pairsdenotes the monomer type and the second number of the pairs denotes themonomer class.

Specific examples of (4,1) monomers preferred for use in the inventioninclude those monomers in Table 9 below.

                  TABLE 9                                                         ______________________________________                                        Monomers of Type 4, Class 1                                                   ______________________________________                                         ##STR106##                                                                   4a                                                                            pyromellitic dianhydride                                                      obtained from Aldrich Chemical Co. and sublimed                               or recrystallized (acetic anhydride) before use.                               ##STR107##                                                                   4b                                                                            1,4,5,8-naphthalenetetracarboxylic dianhydride                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 5 monomers has the general formula ##STR108## wherein Z₈ and Z₉ aredefined as for Z₄ and Z₅ in Table 9. Ar⁵ is defined as in Table 9, thetwo amino groups are ortho to each other, and Z₈, Z₉, and the two aminogroups are positioned such that two imaginary lines drawn perpendicularto the bonds between their valence carbons are collinear.

Formula 5 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (5,1). The number pair (5,1) has the samesignificance as above.

Specific examples of (5,1) monomers preferred for use in the inventioninclude the monomer in Table 10 below.

                  TABLE 10                                                        ______________________________________                                        Monomers of Type 5, Class 1                                                   ______________________________________                                         ##STR109##                                                                   5a                                                                            4,5-diaminonaphthalene-1,8-dicarboxylic anhydride                             prepared from the dinitroderivative by chemical                               reduction according to I. Honda and M. Okazaki,                               J. Soc. Org. Synthetic Chem. (Japan), 7, page 25(1950).                       ______________________________________                                    

Type 6 monomer has the general formula ##STR110## wherein Ar⁶ representsan aromatic moiety and is a tetrahydroxy fused ring system, Z₁₀, Z₁₁,Z₁₂, Z₁₆ are the same HO atoms bonded to carbon atoms of Ar⁶.

In general, Ar⁶ may comprise a single or a plurality of aromatic ringsin the center of a completely conjugated fused ring system. The centeraromatic ring or rings of the completely conjugated fused ring systemcan be any of those described above, and others.

Formula 6 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsobe further classified into two groups: Class 1 (6,1), and Class 2 (6,2).The number pairs have the same significance as above.

The preferred (6,1) monomers are those wherein Ar⁶ comprise a singlecenter aromatic ring in the center of the fused ring system.

The preferred (6,2) monomers are those wherein Ar⁶ comprise at least twocenter aromatic rings in the center of the fused ring system.

Specific examples of (6,1) and (6,2) preferred for use in the inventioninclude those monomers in Tables 11 and 12 respectively.

                  TABLE 11                                                        ______________________________________                                        Monomers of Type 6, Class 1                                                   ______________________________________                                         ##STR111##                                                                   6a                                                                            2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene                               prepared from condensation of 1,2,4,5-                                        tetraaminobenzene with oxalic acid according to                               H. Tadamus, F. DeSchryver, W. DeWinter, and C.                                S. Marvel, J. Polym. Sci. A-1,4, page 2831(1966).                             ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Monomers of Type 6, Class 2                                                   ______________________________________                                         ##STR112##                                                                   6b                                                                            2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline                                     prepared from condensation of 3,3'-diaminobenzidine                           with oxalic acid according to method of                                       H. Tadamus, et al., J. Polym. Sci. A-1,4, page 2831(1966).                    ______________________________________                                    

Type 7 monomer has the general formula ##STR113## wherein Y⁷ representsan aromatic or heteroaromatic moiety and is a fused ring carbon group,and X₇ 's are double bonded to carbon of Y⁷.

Formula 7 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (7,1). The number pair (7,1) has the samesignificance as above.

A specific example of (7,1) preferred for use in the present inventionis 7a in Table 13 below.

                  TABLE 13                                                        ______________________________________                                        Monomers of Type 7, Class 1                                                   ______________________________________                                         ##STR114##                                                                   7a                                                                            1,2,6,7-tetraketopyrene                                                       M. Corell, and H. Streck, Ann. 531, page 6(1937).                             ______________________________________                                    

Type 8 monomer has the general formula ##STR115## wherein Y⁸ is a singlecarbon cyclic moiety, X₁₀ and X₁₁ are HO and O atoms respectively,bonded to carbon atoms of Y⁸.

Formula 8 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (8,1). The number pair (8,1) has the samesignificance as above.

A specific example of (8,1) preferred for use in the present inventionis 8a in Table 14 below.

                  TABLE 14                                                        ______________________________________                                        Monomers of Type 8, Class 1                                                   ______________________________________                                         ##STR116##                                                                   8a                                                                            2,5-dihydroxy-1,4-benzoquinone                                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 9 monomers has the general formula ##STR117## wherein Ar⁹represents an aromatic moiety and is a partially fused ring system, Z₁₄and Z₁₅ are OH atoms, X₄ are selected from the class O, S, and NR; R isH or an organic group attached to N; NH₂, X₄ H, Z₁₄, and Z₁₅ are bondedto carbon atoms of Ar⁹ ; NH₂ and X₄ H are positioned ortho; Z₁₄ and Z₁₅are positioned ortho.

Formula 9 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the pesent invention can beclassified as Class 1 (9,1). The number pair (9,1) has the samesignificance as above.

A specific example of (9,1) preferred for use in the present inventionis 9a in Table 15 below.

                  TABLE 15                                                        ______________________________________                                        Monomers of Type 9, Class 1                                                   ______________________________________                                         ##STR118##                                                                   9a                                                                            2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride                          prepared from 1,2-diamino-4,5-dinitrobenzene by                               condensation with oxalic acid followed by reduction                           according to R. F. Kovar and F. E. Arnold,                                    J. Polym. Sci., Polym. Chem. Ed., 14, page 2807(1976).                        ______________________________________                                    

All of the above-cited patents and/or publications of Tables 1-15 arespecifically incorporated herein by reference.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas I-VIII homopolymers may be illustrated bythe following general reaction system: ##STR119##

Representative examples of suitable homopolymers forming liquidcrystalline homopolymer compositions in accordance with the practice ofthe present invention (provided they fall within the above-definedgeneral formulas I-VIII) include the following polymers. For the sake ofconvenience, polymer formulas are hereinbelow shown in simplifiedrepresentation. As an example, --AI]_(n) is ##STR120## The structuresrepresenting --AI] are defined in the Appendix --A] has the structure##STR121## and --I] has the structure ##STR122##

Their sequential combination is therefore ##STR123## All simplifiedpolymer formula representations appearing in the specification may bereadily interpreted by reference to the Appendix.

--AI]_(n), --AIBI]_(n), --BI]_(n), and --T]_(n),

--AIDI]_(n), --AIEI]_(n), --AIFI]_(n), --AILI]_(n), --AIMI]_(n),--AINI]_(n),

--ATIT']_(n), --ATKT']_(n), --BIDI]_(n), --BIEI]_(n), --BIFI]_(n),

--BILI]_(n), --BIMI]_(n), --BINI]_(n), --BTIT']_(n), --BTKT']_(n),

--EILI]_(n), --FILI]_(n), --LI]_(n), --TI]_(n), --U]_(n), and --V]_(n),

--A]_(n), --AB]_(n), --AC]_(n), --AE]_(n), --AF]_(n), --AICI]_(n)--AIOI]_(n),

--AIQI]_(n), --AJ]_(n), --AL]_(n), --AM]_(n), --AN]_(n), --AQ]_(n),--AVIV']_(n),

--B]_(n), --BC]_(n), --BD]_(n), --BE]_(n), --BF]_(n), --BICI]_(n),--BIOI]_(n),

--BIQI]_(n), --BJ]_(n), --BL]_(n), --BM]_(n), --BN]_(n), --BQ]_(n),--BVIV']_(n),

--B'A'B'Z]_(n), --B'A'F'Z]_(n), --B'H']_(n) * (* denotes oxygens alwaysmeta on B') --B'I']_(n), --B'P']_(n),

--B'Q']_(n), --B'S']_(n) * --C]_(n), --CE]_(n), --CF]_(n), --CI]_(n),--CIEI]_(n),

--CIFI]_(n), --CILI]_(n), --CIMI]_(n), --CINI]_(n), --CIOI]_(n),--CJ]_(n),

--CL]_(n) --CM]_(n), --CN]_(n), --CTIT']_(n), --CTKT']_(n),--C'A'B'Z]_(n),

--C'A'F'Z]_(n), --D'A'B'Z]_(n), --D'A'F'Z]_(n), --E]_(n), --EF]_(n),

--EI]_(n), --EIFI]_(n), --EIMI]_(n), --EINI]_(n), --EIOI]_(n),--EIQI]_(n),

--EJ]_(n), --EL]_(n), --EM]_(n), --EN]_(n), --ETIT']_(n), --ETKT']_(n),

--E'A'B'Z]_(n), --E'A'F'Z]_(n), --F]_(n), --FI]_(n), --FIMI]_(n),

--FINI]_(n), --FIOI]_(n), --FJ]_(n), --FL]_(n), --FM]_(n), --FN]_(n),--F'A']_(n),

--L]_(n), --LJ]_(n), --LTIT']_(n), --LTKT']_(n), --M]_(n), --MI]_(n),--MTIT']_(n),

--MTKT']_(n), --N]_(n), --NI]_(n), --NTIT']_(n), --NTKT']_(n),--QI]_(n),

--QJ]_(n), --RI]_(n), --RJ]_(n), and --UI]_(n),

--AD]_(n), --AG]_(n), --AH]_(n), --AIGI]_(n), --AIHI]_(n), --AIPI]_(n),

--AIRI]_(n), --AISI]_(n), --AK]_(n), --AO]_(n), --AP]_(n), --AR]_(n),--AS]_(n), --BG]_(n),

--BIGI]_(n), --BH]_(n), --BIHI]_(n), --BIPI]_(n), --BIRI]_(n),--BISI]_(n),

--BK]_(n), --BO]_(n), --BP]_(n), --BR]_(n), --BS]_(n), --B'G']_(n),

--B'H']_(n) ** (** denotes oxygen always para on B'),

--B'J']_(n), --B'K']_(n) * (* denotes oxygens always meta on B'),

--B'K']_(n) **, --B'L']_(n), --B'M']_(n), --B'N']_(n), --B'O']_(n),

--B'R']_(n), --B'S']_(n) **, --B'U']_(n), --CD]_(n), --CG]_(n),--CH]_(n),

--CIDI]_(n), --CIGI]_(n), --CIHI]_(n), --CIPI]_(n), --CIQI]_(n),--CIRI]_(n),

--CISI]_(n), --CK]_(n), --CO]_(n), --CP]_(n), --CQ]_(n), --CR]_(n),--CS]_(n),

--CVIV']_(n), --C'G']_(n), --C'H']_(n), --C'I']_(n), --C'J']_(n),--C'K']_(n),

--C'L']_(n), --C'O']_(n), --C'Q']_(n), --C'R']_(n), --C'S']_(n),

--D]_(n), --DE]_(n), --DF]_(n), --DG]_(n), --DH]_(n), --DI]_(n),--DIEI]_(n),

--DIFI]_(n), --DIGI]_(n), --DIHI]_(n), --DILI]_(n), --DIMI]_(n),--DINI]_(n),

--DIOI]_(n), --DIPI]_(n), --DIQI]_(n), --DIRI]_(n), --DISI]_(n),

--DJ]_(n), --DK]_(n), --DL]_(n), --DM]_(n), --DN]_(n), --DO]_(n),--DP]_(n),

--DQ]_(n), --DR]_(n), --DS]_(n), --DTIT']_(n), --DTKT']_(n),--DVIV']_(n),

--D'G']_(n), --D'H']_(n) * (* denotes oxygen always in 3,3'-positions onD'), --D'H']_(n) ** (** denotes oxygen always in 4,4'-positions on D'),

--D'I']_(n), --D'J']_(n), --D'K']_(n) *, --D'K']_(n) **,

--D'L']_(n), --D'M']_(n), --D'N']_(n), --D'O']_(n), --D'Q']_(n),--D'R']_(n),

--D'S']_(n) *, --D'S']_(n) **, --D'U']_(n), --EG]_(n), --EH]_(n),--EIGI]_(n),

--EIHI]_(n), --EIPI]_(n), --EIRI]_(n), --EISI]_(n), --EK]_(n),--EO]_(n),

--EP]_(n), --EQ]_(n), --ER]_(n), --ES]_(n), --EVIV']_(n), --E'G']_(n),

--E'H']_(n), --E'I']_(n), --E'J']_(n), --E'K']_(n), --E'L']_(n),--E'O']_(n),

--E'Q']_(n), --E'R']_(n), --E'S']_(n), --FG]_(n), --FR]_(n),

--FIGI]_(n), --FIHI]_(n), --FIPI]_(n), --FIQI]_(n), --FIRI]_(n),--FISI]_(n),

--FK]_(n), --FO]_(n), --FP]_(n), --FQ]_(n), --FR]_(n), --FS]_(n),--FTIT']_(n),

--FTKT']_(n), --FVIV']_(n), --G]_(n), --GH]_(n), --GI]_(n), --GIHI]_(n),

--GILI]_(n), --GIMI]_(n), --GINI]_(n), --GIOI]_(n), --GIPI]_(n),--GIQI]_(n),

GIRI]_(n), --GISI]_(n), --GJ]_(n), --GK]_(n), --GL]_(n), --GM]_(n),--GN]_(n),

--GO]_(n), --GP]_(n), --GQ]_(n), --GR]_(n), --GS]_(n), --GTIT']_(n),

--GTKT']_(n), --GVIV']_(n), --H]_(n), --HI]_(n), --HILI]_(n),

--HIMI]_(n), --HINI]_(n), --HIOI]_(n), --HIPI]_(n), --HIQI]_(n),--HIRI]_(n),

--HISI]_(n), --HJ]_(n), --HK]_(n), --HL]_(n), --HM]_(n), --HN]_(n),--HO]_(n),

--HP]_(n), --HQ]_(n), --HR]_(n), --HS]_(n), --HTIT']_(n),

--HTKT']_(n), --HVIV']_(n), --LK]_(n), --LVIV']_(n),

--MJ]_(n), --MK]_(n), --MVIV']_(n), --NJ]_(n), --NK]_(n),

--NVIV']_(n), --OI]_(n), --OJ]_(n), --OK]_(n), --OTIT']_(n),

--OTKT']_(n), --OVIV']_(n), --PI]_(n), --PJ]_(n), --PK]_(n),

--PTIT']_(n), --PTKT']_(n), --PVIV']_(n), --Q]_(n), --QK]_(n),

--QTIT']_(n), --QTKT']_(n), --QVIV']_(n), --R]_(n), --RK]_(n),

--RTIT']_(n), --RTKT']_(n), --RVIV']_(n), --SI]_(n), --SJ]_(n),

--SK]_(n), --STIT']_(n), --STKT']_(n), --SVIV']_(n), --W]_(n),

--X]_(n), and --Y]_(n).

The most preferred extended chain homopolymers in accordance with thepractice of the present invention include

--AI]_(n), --AIBI]_(n), --BI]_(n), and --T]_(n).

The especially preferred extended chain homopolymers in accordance withthe practice of the present invention include

--AIDI]_(n), --AIEI]_(n), --AIFI]_(n), --AILI]_(n), --AIMI]_(n),--AINI]_(n),

--ATIT']_(n), --ATKT']_(n), --BIDI]_(n), --BIEI]_(n), --BIFI]_(n),

--BILI]_(n), --BIMI]_(n), --BINI]_(n), --BTIT']_(n), --BTKT']_(n),

--EILI]_(n), --FILI]_(n), --LI]_(n), --TI]_(n), --U]_(n), and --V]_(n).

The preferred extended chain homopolymers in accordance with thepractice of the present invention include

--A]_(n), --AB]_(n), --AC]_(n), --AE]_(n), --AF]_(n), --AICI]_(n),--AIOI]_(n),

--AIQI]_(n), --AJ]_(n), --AL]_(n), --AM]_(n), --AN]_(n), --AQ]_(n),--AVIV']_(n),

--B]_(n), --BC]_(n), --BD]_(n), --BE]_(n), --BF]_(n), --BICI]_(n),--BIOI]_(n),

--BIQI]_(n), --BJ]_(n), --BL]_(n), --BM]_(n), --BN]_(n), --BQ]_(n),--BVIV']_(n),

--B'A'B'Z]_(n), --B'A'F'Z]_(n), --B'H']_(n) * (* denotes oxygens alwaysmeta on B') --B'I']_(n), --B'P']_(n),

--B'Q']_(n), --B'S']*--C]_(n), --CE]_(n), --CF]_(n), --CI]_(n),--CIEI]_(n),

--CIFI]_(n), --CILI]_(n), --CIMI]_(n), --CINI]_(n), --CIOI]_(n),--CJ]_(n),

--CL]_(n), --CM]_(n), --CN]_(n), --CTIT']_(n), --CTKT']_(n),--C'A'B'Z]_(n),

--C'A'F'Z]_(n), --D'A'B'Z]_(n), --D'A'F'Z]_(n), --E]_(n), --EF]_(n),

--EI]_(n), --EIFI]_(n), --EIMI]_(n), --EINI]_(n), --EIOI]_(n),--EIQI]_(n),

--EJ]_(n), --EL]_(n), --EM]_(n), --EN]_(n), --ETIT']_(n), --ETKT']_(n),

--E'A'B'Z]_(n), --E'A'F'Z]_(n), --F]_(n), --FI]_(n), --FIMI]_(n),

--FINI]_(n), --FIOI]_(n), --FJ]_(n), --FL]_(n), --FM]_(n), --FN]_(n),--F'A']_(n),

--L]_(n), --LJ]_(n), --LTIT']_(n), --LTKT']_(n), --M]_(n), --MI]_(n),--MTIT']_(n),

--MTKT']_(n), --N]_(n), --NI]_(n), --NTIT']_(n), --NTKT']_(n),--QI]_(n),

--QJ]_(n), --RI]_(n), --RJ]_(n), and --UI]_(n).

It is helpful to define three P₂ O₅ contents, operative at differentstages of polymerization, that must be controlled in order to optimizethe synthesis procedure of the present invention. We will define theinitial P₂ O₅ content m_(o) as the P₂ O₅ content of the polyphosphoricacid operative during dehydrohalgenation (in step b above and asexplained more fully hereinafter). The initial P₂ O₅ content inaccordance with the practice of the instant invention should be belowabout 83.3%, and may range from between about 83.3% to about 63%;preferrably below about 82%, more preferrably below about 80%, and mostpreferrably below about 76%.

The intermediate P₂ O₅ content is operative at the initiation ofpolycondensation and is calculated so as to give the third (or final) P₂O₅ content f that accounts for polyphosphoric acid hydrolysis by 100% ofthe theoretical water of polycondensation. The final P₂ O₅ content, f,must be above some minimum value if the solution is to maintain itseffectiveness as a reaction medium at the late stages of polymerization.The final P₂ O₅ content should be between about 82% to about 86%,preferrably between about 82% to about 84%, and most preferrably betweenabout 82% to about 83%.

The various important general process steps for preparing liquidcrystalline polymer compositions of the present invention may includeone or more of the following stages which are considered to be withinthe process parameters described above. These stages are:

Stage One--One or more of a selected first monomers selected from thegroup consisting of (amino-group-containing) monomers 1, 3, 5, or 9 isadded to a specified initial weight in grams (given by a*) of apolyphosphoric acid with a P₂ O₅ content m_(o) according to theempirical equation

    a* ={[1-f]([P.sub.y /P.sub.c ]-P.sub.y)-[n.sub.o (18.02)/M.sub.w ]P.sub.y }(1-m.sub.o).sup.-1

where P_(y) is the weight in grams of the theoretical yield of polymer,P_(c) is the weight fraction of polymer in the total weight of the finalliquid crystalline polymer composition (and is chosen to be above thecritical concentration of the polymer necessary for liquid crystallinephase formation in the resulting polymer-polyphosphoric acidcomposition), n_(o) is an integer giving the number of moles ofcondensation by-product per mole of polymer repeating unit, the number18.02 is the molecular weight of the condensation by-product, M_(w) ismolecular weight of the polymer repeating unit, and f is the final P₂ O₅content that must be above a minimum value as defined by this invention.

Stage Two--Once the first monomer(s) are combined with polyphosphoricacid, and protecting groups, if present, released, (optionally,depending on the particular polymer and reaction mechanism chosen) astoichiometric amount of one or more of a selected second monomersselected from the group consisting of 2, 4, 6, 7 or 8 is next added andthe chosen value of f is achieved by adding b* (an intermediate weightin grams of P₂ O₅) to the mixture according to the equation.

    b* =[P.sub.y /P.sub.c ]-P.sub.y -[{n.sub.o (18.02)/M.sub.w }]P.sub.y -a*

Stage Three--The resulting mixture (containing the first monomer(s)and/or the second monomer(s)) is then heated to a temperature suitablefor polycondensation. The reaction temperature may range from about 100°C. to about 210° C., preferrably about 110° C. to about 200° C. morepreferrably about 160° C. to about 190° C., and most preferrably about185° C.

The P₂ O₅ content, m_(o), should be low enough to:

(1) achieve efficient dehydrohalogenation and/or

(2) achieve sufficient monomer loading to achieve desired P_(c) withoutfoaming problem or unusually high bulk viscosity. f should be highenough to:

(2a) maintain a polyphosphoric acid composition that is an effectivereaction medium at late stages of polycondensation.

(2b) provide an effective phosphorylating medium as described in N. Yodaand M. Kurihara, "New Polymers of Aromatic Heterocycles byPolyphosphoric Acid Solution Methods", J. Polymer Science,Macromolecular Reviews, Volume 5, (1971), p. 159 at initial stage ofpolymerization. The subject matter of the paper by Yoda and et. al., isspecifically incorporated herein by reference.

(2c) provide an effective solvent for the polymer at the end ofpolycondensation.

For purpose of illustration, a plot of equation a* is presented in FIG.7 showing regions (shaded dash area) of poor monomer 1a solubility. Inthe case of polymer --AI]_(n), the family of P_(c) curves can beutilized as follows:

1. choose a --AI]_(n) polymer concentration, P_(c), as an example 0.16;

2. select a point on the curve P_(c) =0.16 above the shaded dash areaindicating poor monomer 1a solubility;

3. from that point selected, the weight in grams of PPA (a*) of thecorresponding P₂ O₅ content (m_(o)) that should be added to 92.06 g ofmonomer 1a can be determined;

4. after dehydrochlorination is complete, the amount of monomer 2a to beadded is 62.38 g; and

5. if the final P₂ O₅ content (f) has been chosen to be 82.2%, then theamount of P₂ O₅ to be added (b*) is the difference between the amount ofPPA used in step 3 above and the weight of PPA at the end of the curvefor P_(c) =0.16.

The choice of the optimal m_(o) is depentent on the desired polymerconcentration and the solubility limits of the first monomer. The regionof poor solubility for monomer 1a is shown in FIG. 7. Other monomersexhibit different solubility limits. Solubility rankings of somerepresentative monomers are listed below.

monomers with solubilities greater than 1a;

1f, 1g, 3a, 3b, 3c, and 3d;

monomers with solubilities comparable to 1a:

1d, and 3e;

monomers with solubilities less than 1a:

1b, 1c; 1e, 1i, 1k, 3f, 3g, 3h, 3i, and 3j;

and monomers with solubilities much less than 1a:

1h, 1l, 1m, 1n, 1o, 1p, 5a, and 9a.

Accordingly, it is possible to dehydrohalogenate the selectedhydrohalide (monomers) more rapidly; the foaming problem is alleviatedor eliminated; the solution in PPA of lesser P₂ O₅ content than that ofU.S. Pat. No. 4,225,700 is much less viscous and dehydrohalogenation canbe carried out much more readily. Further, a solution of selectedmonomers in PPA of considerably higher concentration is possible and areaction product containing a much higher concentration of polymer ispossible.

The above-mentioned formulas I, III, V, VII, and VIII homopolymercompositions may be prepared in accordance with the above processparameters by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (1,1), (1,2), or (1,3)with or without oxidation protecting atoms or groups with a preliminarysolvent of phosphoric acid having a relatively low phosphorus pentoxidecontent,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding a selected second monomer (for example, a second monomerselected from the group consisting of (2,1), (2,2), (2,3), (4,1), (6,1),(6,2), (7,1) or (8,1)) in the resulting mixture of step (b) to provide amixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization.

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect radiation at a rate to form a firsthomooligomeric product having a preselected intrinsic viscosity or afirst homopolymeric product.

Formulas II, IV, and VI homopolymer compositions may be prepared by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (3,1), (3,2), (5,1), or(9,1) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent.

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homooligomericproduct having a preselected intrinsic viscosity or a firsthomopolymeric product.

Copolymeric Compositions and their preparation

In accordance with a further aspect of the invention, there is provideda liquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain copolymer having thegeneral formulas: ##STR124## wherein Ar¹ represents an aromatic moietyand is XXX as defined above, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, and Y² is nil or represents a bivalent organic radical and isXXXI as defined above, a_(i) b_(i) represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR125## wherein Ar¹ represents an aromatic moiety and is XXXas defined above, X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ orX₂ of each hetero ring are disposed ortho to one another and Y²represents a bivalent organic radical and is XXXI as defined above,a_(i) b_(i) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, Ar³ represents a different aromatic moietyand is XXII as defined above, the nitrogen atom and X₃ being bonded toaromatic carbon atoms of Ar³, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR126## wherein Ar³ represents an aromatic moietyand is XXII as defined above, X₃ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₃ being bonded toaromatic carbon atoms of Ar³, N and X₃ of each hetero ring are disposedortho to one another, c_(k) represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;##STR127## wherein Ar¹ represents an aromatic moiety and is XXXII asdefined above, Ar⁴ represents a different aromatic moiety and is XXIIIas defined above, the nitrogen atoms being bonded to Ar¹ and the carbonatoms being bonded to Ar⁴, a_(i) b_(j) represents the molar proportionsof the respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR128## wherein Ar⁴ represents a different aromatic moietyand is XXIII as defined above, Ar¹ represents an aromatic moiety and isXXXII as defined above, and Ar⁵ represents an aromatic moiety differentfrom Ar⁴ and Ar¹ and is XXIV as defined above, the carbon atoms beingbonded to Ar⁴ and Ar⁵ and the nitrogen atoms being bonded to Ar¹ andAr⁵, n being a positive integer; c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, a_(i)b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer; ##STR129##wherein Ar¹ represents an aromatic moiety and is XXX as defined above,Ar⁶ represents a different aromatic moiety and is XXV as defined above,X₁ and X₂ are the same or different and are sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the NH groups and X₄ and X₁ beingbonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of eachhereto ring are disposed ortho to one another, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR130## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, Ar⁶ represents adifferent aromatic moiety and is XXV as defined above, X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hereto ring aredisposed ortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar⁹represents an aromatic moiety different from Ar⁶ and Ar¹ and is XXVI asdefined above, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(k) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; or ##STR131## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Y⁷ represents an aromatic or heteroaromaticmoiety and is XXVIII as defined above, the nitrogen atoms being bondedto aromatic carbon atoms of Ar¹ and bonded to adjacent carbon atoms ofY⁷, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XVIII copolymers may be illustrated bythe following general reaction system: ##STR132## The above-mentionedformulas IX, X, XII, XV, XVI, XVII, and XVIII copolymer compositions maybe prepared in accordance with the above process parameters by:

(a) mixing at least two of a selected first monomers (for example, twoor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting mixture ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Similarly formulas IX, XII, XVIII, and copolymer compositions may beprepared by:

(a) mixing at least one of a selected first monomers (for example, oneor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least two of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting mixture ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstcooligomeric product having a preselected intrinsic viscosity or a firstcopolymeric product.

Preferred formulas IX, X, XI, XII, XV, XVI, XVII, and XVIII, andcopolymers forming liquid crystalline copolymer compositions of theinstant invention are those wherein a_(i) is the mole fraction of theith monomer selected from Type 1, b_(j) is the mole fraction of the jthmonomer selected from Types 2, 4, 6, 7, or 8, c_(k) is the mole fractionof the kth monomer selected from Types 3, 5, or 9, m and m' areappropriate molar quantities based on desired yiled, a_(i) b_(j) anda_(i) b_(j) m/m+m' are the molar proportions of the recurring unitsresulting from the condensation of the ith monomer of Type 1 and the jthmonomer of Type 2, 4, 6, 7, or 8, c_(k) and c_(k) m'/m+m' are the molarproportions of the recurring unit resulting from the condensation of thekth monomer of Type 3, 5, or 9, y_(ij) is the average block length(i.e., the average number of sequential recurring units unbroken by adifferent recurring unit) of the recurring unit formed from the ithmonomer of Type 1 and the jth monomer of Type 2, 4, 6, 7, or 8, y_(k) isthe average block length of the recurring unit formed byself-condensation of the kth monomer of Type 3, 5, or 9, and n is theaverage overall length of the copolymer (i.e., the average total numberof recurring units independent of structure). The number of recurringunits in the copolymer may be the product of the highest i and thehighest j or may be the product of the highest i and the highest j plusthe highest k. i, j and k can be as high as is practical, but may havecertain minimal values if copolymers, rather than homopolymers, are tobe obtained.

Selected molar quantities (a₁ m, a₂ m, . . . a_(i) m) of monomers ofType 1 may be mixed with a phosphoric acid having a phosphorus pentoxidecontent of from about 63% to about 78%, preferably greater than about68%, most preferably about 78%, and the protecting groups, such ashydrogen halide, if present, may be substantially removed by heating,and applying reduced pressure if desired. The quantity of the phosphoricacid is most desirably determined in accordance with equation a* above,making the necessary calculations for addition of monomers of possiblydifferent molecular weights and different proportions. A stoichiometricquantity (i.e., b₁ m+b₂ m+. . . b_(j) m=m) of monomer selected from Type2, 4, 6, 7, or 8 may then be added to the resulting solution. Thephosphorus pentoxide content of the resulting mixture may then be raisedin accordance with equation b* above, so as to raise the finalphosphorus pentoxide content of the substantially copolymerized mixtureto a value preferably within the range between about 81% to about 84%and most preferably between about 82% to about 83.5%. The resultingmixture may then be heated to a temperature preferably about 100° C. toabout 210° C., most preferably to about 170° C. to about 185° C. withina practical time period, from less than about one hour to greater thanabout 5 hours, preferably within about 1 to about 3 hours. Thetemperature may be maintained for a sufficient time, which may rangefrom less than about 1 hour to about 48 hours or more, most preferablybetween from about 1 to about 23 hours, to achieve the desired n value.The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions comprising copolymers with thegeneral formulas IX, XII, XVI, and XVIII is illustrated for thosecompositions including general formula IX wherein the selected monomersof Type 1 are further classified as being of Types (1,1), (1,2), or(1,3) and the selected monomers of Type 2 are of Types (2,1), (2,2), or(2,3).

General formula IX copolymers prepared from Type (1,1), and Type (2,1)monomers have the advantage that the critical concentration necessaryfor liquid-crystalline behavior is low. For the copolymers listed below,their critical concentration may be as low as about 5 weight percent inpolyphosphoric acid at substantially moderate n values, thus allowing abroad range of operable concentrations. ##STR133## Since the recurringunits of the copolymers are of essentially comparable mesogenicity, abroad range of copolymer compositions may be achieved; for instance, a₁b₁ can range from nearly zero to nearly one while a_(i) b₂ or a₂ b₁(because it is equal to 1-a₁ b₁) ranges from nearly one to nearly zero,respectively. The average block lengths y₁₁ and y₁₂ or y₂₁ are governedby the method of monomer addition described above and the molarquantities selected. Thus, for monomer pairs of essentially equalreactivity, y₁₁, which equals 1/1-a₁ b₁, may range from nearly one tovery high values. In a like manner, y₁₂ or y₂₁ can range from very highvalues to nearly one. Monomer purity, control of stoichiometry, andexclusion of side reactions caused by oxidizing impurities must besufficient to obtain an overall copolymer length, n, greater than about50 in order to obtain the desired polymeric properties of usefulmechanical strength, modulus, etc. The practice of the invention as itrelates to copolymers derived from Class 1 monomers is furtherillustrated in Examples 49-51 and 54-66 below.

General formula IX copolymers may be prepared from type (1,1) (2,1) and(2,2) monomers and from type (1,1), (1,2) and (2,1) monomers. Thesemonomers are classified as Class 2 owing either to a moderately reducedmesogenic character of the recurring unit derived from them or to theirtendency to reduce the solubility range of the resulting polymer, whichin turn is usually owing to an overall reduction of theheteroatom/hydrocarbon ratio of the resulting polymer. Both of theseconditions dictate that incorporation of Class 2 monomers intocopolymers of the present invention should be carefully selected. Thedegree of this selectivity is illustrated by the following copolymersprepared in accordance with the practice of the invention. ##STR134##The immediately preceding list of copolymers is derived from monomercompositions containing monomers imparting reduced solubility to thecopolymer. The preferred values of a₁ b₁ (i.e., the mole fraction of themore soluble recurring unit) are those greater than about 0.8, leadingto values of y₁₁ greater than about 5 and y₁₂ values of nearly one.Monomer purity, control of stoichiometry, exclusion of oxidizingimpurities, and selection of the molar quantity of the less solublemonomer to maintain copolymer solubility must be sufficient to achievean average n value of greater than about 50. Increased proportion of aless soluble monomer may be achieved by selecting comonomers that impartimproved solubility to the copolymer. In general, monomers of Type 1wherein X is S impart greater solubility than those in whic X is O or N.The practice of the invention as it relates to copolymers of partiallyreduced solubility is further illustrated in Examples 52, 53, 70, 71,and 72 below.

The following list of copolymers is derived from incorporation ofmonomers of moderately reduced mesogenicity and the practice of theinvention is illustrated for them. ##STR135## The preferred ranges of a₁b₁ are from nearly zero to nearly one for copolymers in thisclassification with the overall proviso that the overall copolymerconcentration in the polyphosphoric acid be above a criticalconcentration determined by the least mesogenic recurring unit. Thus,above about 13% the above copolymers may have a₁ b₁ values between aboutone and zero, y₁₁ values of nearly one and greater, and y₂₁ values ofnearly one and greater. The preferred concentration with these a₁ b₂ anda₂ b₁ values may be between about 15 and about 22 weight percent. If themolar proportion of the more highly mesogenic recurring unit (i.e., a₁b₁) is selected to have values of greater than about 0.6, preferablygreater than about 0.75, then the range of operable concentrations isincreased to include concentrations of the copolymer in greater thanabout 8 weight percent, preferably above about 10 weight percent. Valuesof n greater than about 50 are preferable as stated above.

General formula IX copolymer compositions may be prepared from Class 3monomers.

Monomers characterized as belonging to Class 3 lead to polymer recurringunits that have little or no mesogenic character. Their incorporationinto copolymers prepared as above are within the scope of the presentinvention but are less preferred because the random incorporation of asignificant molar proportion of these nonmesogenic units leads toinsufficient block length of the mesogenic recurring unit or units toimpart liquid-crystalline behavior. Incorporation of less than about 3molar percent of Class 3 monomers is preferred. Increased incorporationof Class 3 polymers are highly preferred by use of a block polymerprocedure described below. A less preferred embodiment of the presentinvention is the preparation of General formulas X, XV, and XVII by theaddition of monomers of Types 3, 5, and 9, respectively, to the initialsolution of the above copolymer procedure. The unique feature of thegeometry of monomers of Types 3 (except for 3k), 5, and 9 is therequirement that the block lengths, y_(k), be large or, if small, be aneven number. This condition dictates that preferred compositions offormulas X, XV, and XVII are prepared by a block polymer proceduredescribed below.

The general formula XI copolymer composition shown above is preparedaccording to the following procedure:

(a) mixing at leat two of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Selected molar quantities (c₁ m, c₂ m, . . . c_(k) m) of Type 3 monomersmay be mixed with a phosphoric acid having a phosphorus pentoxidecontent of from about 63% to about 78%, preferably greater than about68%, most preferably about 78%, and the protecting groups, if present,may be substantially removed by heating, and applying reduced pressure,if desired. The quantity of phosphoric acid is determined in accordancewith equation a* above, making the necessary calculations for theaddition of monomers of possibly different molecular weights anddifferent proportions. The phosphorus pentoxide content of the resultingmixture may then be raised in accordance with equation b* above, so asto raise the final phosphorus pentoxide of the substantiallycopolymerized mixture to a value greater than about 81%, most preferablybetween about 82% to about 83% but less than about 84%. The resultingmixture may then be heated to about 100° C. to about 200° C., mostpreferably between about 150° C. to about 185° C. within a practicalperiod of time, preferably within a time period of less than about 1hour to about 5 hours or more, and most preferably within a period ofabout 1 hour to about 3 hours, and then maintained at the selectedtemperature for sufficient time to achieve the desired n value.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include copolymers with thegeneral formula XI is further illustrated for those compositions whereinthe selected monomers of Type 3 are further classified as being of Type(3,2).

The polymers ##STR136## are prepared according to the above procedurewherein c₁ is the molar proportion of the more soluble recurring unitand selected to be above about 0.5, more preferably above about 0.7, toensure the solubility of the resulting copolymer to the highconcentrations required for liquid-crystalline behaviour. A weightpercent of the copolymer above about 15 weight percent, more preferablyabove about 17.5 weight percent, may be selected. Molar proportionsselected above and monomer reactivity ratios determine the average blocklengths y₁ and y₂. The block length does not bear on whetherliquid-crystalline behavior in polyphosphoric acid is obtained withthese polymers. The important factor is the maintenance of solubility athigh concentration and the preparation of these copolymers inpolyphosphoric acid at high concentration from monomers.

Blockpolymeric Compositions and their preparation

In accordance with a still further aspect of the invention, there isprovided a liquid-crystalline composition useful in the preparation offibers and films comprising a polycondensation product consistingessentialy of a blend of certain polyphosphoric acids and a highconcentration of at least one high molecular weight extended chain blockpolymer having the general formulas: ##STR137## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR138## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar³ represents an aromatic moiety and is XXII as definedabove, X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₃ being bonded to aromatic carbon atomsof Ar¹, N and X₃ of each hetero ring are disposed ortho to one another,c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR139## wherein Ar³ represents an aromatic moiety and isXXII as defined above, X₃ is sulfur, oxygen, or NR (R being hydrogen oran organic group), the nitrogen atoms and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of each hetero ring are disposed ortho toone another, c_(k) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR140## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Ar⁴ represents a different aromatic moiety andis XXIII as defined above, the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR141## wherein Ar¹ represents an aromaticmoiety and is XXXII or XXX as defined above with the proviso that whenAr¹ is bonded to nitrogen atoms Ar¹ is XXXII and when Ar¹ is bonded toboth nitrogen atoms and X₁ and X₂, Ar¹ is XXX as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the carbon atoms being bonded to Ar⁴, m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y' represents an average number of the respectivedifferent sequential recurring units present in said block polymer, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar⁴, N and X₁ and X₂ of each heteroring are disposed ortho to one another and Y² is nil or represents abivalent organic radical and is XXXI as defined above, m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR142## wherein Ar³ representsan aromatic moiety and is XXII as defined above, X₃ is sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, p represents the molarproportions of the respective different recurring units present in saidblock polymer, y'/2 represents an average number of the respectivedifferent sequential recurring units present in said block polymer, Ar¹represents an aromatic moiety and is XXXII as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, q represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer; ##STR143## wherein Ar⁴represents a different aromatic moiety and is XXIII as defined above,Ar¹ represents an aromatic moiety and is XXXII as defined above, and Ar⁵represents an aromatic moiety different from Ar⁴ and Ar¹ and is XXIV asdefined above, the carbon atoms being bonded to Ar⁴ and Ar⁵ and thenitrogen atoms being bonded to Ar¹ and Ar⁵, n being a positive integer;c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR144## wherein Ar¹represents an aromatic moiety and is XXX as defined above, Ar⁶represents a different aromatic moiety and is XXV as defined above, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR145## wherein Ar¹ represents an aromaticmoiety and is XXX as defined above, Ar⁶ represents a different aromaticmoiety and is XXV as defined above, X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the NH groups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶and Ar¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, Ar⁹ representsan aromatic moiety different from Ar⁶ and Ar¹ and is XXVI as definedabove, X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₄ being bonded to aromatic carbon atoms ofAr⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; or ##STR146## wherein Ar¹ represents an aromaticmoiety and is XXXII as defined above, Y⁷ represents an aromatic orheteroaromatic moiety and is XXVIII as defined above, the nitrogen atomsbeing bonded to aromatic carbon atoms of Ar¹ and bonded to adjacentcarbon atoms of Y⁷, a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XIX block polymers may be illustratedby the following general reaction system: ##STR147## The above-mentionedformulas IX, XII, XVI, XVIII, and XIX block polymer compositions may beprepared in accordance with the above process parameters by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of the first and second monomerin the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), (d),and (e) with the overall proviso that at least one of the selectedmonomer of step (a) or (c) which forms the second homo-oligomericproduct be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, formulas IX, XII, XVI, XVIII, and XIX block polymercompositions may be prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a first mixture of the first and secondmonomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of a different first and secondmonomer in the preliminary solvent, said second mixture being formed bylike steps (a), (b) and (c) with the overall proviso that at least oneof the selected monomer of step (a) or (c) which forms the secondmixture be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (f) to provide a first oligomer-monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(h) causing polymerization of the mixture resulting from step (g) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The above IX-XIX block polymers forming the liquid crystalline blockpolymer compositions of the instant invention can be characterized ashaving more than one recurring unit, the distribution or sequencing ofwhich may be different from that obtained by the random condensation ofmonomers as in the copolymers described above and is furthercharacterized as having contiguous blocks of the same recurring unit asobtained by the random condensation of oligomers.

The preferred formulas IX, XII, XVI, XVIII, and XIX block polymers arethose polymers wherein a_(i) b_(j) is the mole fraction of the recurringunit formed by the condensation of a homo-oligomeric reaction product(defined below) derived from the ith monomer of Type 1 with astoichiometric quantity of jth monomer of Type 2, 4, 6, 7, or 8,respectively, and incorporated by a block-polymeric procedure describedbelow, and y_(ij) and n have the same meaning as described above forcopolymers.

The preferred XI block polymers are those wherein c_(k) is the molefraction of the recurring unit formed by the condensation of ahomo-oligomeric reaction product (defined below) derived from the kthmonomer of Type 3 and incorporated by a block polymeric proceduredescribed below, and y_(k) and n are as defined for copolymers.

The preferred X, XV, and XVII block polymers are those wherein a_(i)b_(j) m/m+m' is the mole fraction of the recurring unit formed by thecondensation of m moles of recurring units of a homo-oligomeric reactionproduct derived from the ith monomer of Type 1 and the jth monomer ofType 2, 4, or 6 and combined with m' moles of recurring units of ahomo-oligomeric reaction product derived from condensation of the kthmonomer of Type 3, 5, or 9, respectively, and y_(ij), y_(k), and n areas defined for copolymers.

The preferred XIII block polymers are those wherein m' and m areappropriate molar quantities of the monomers that form the reactionproducts and are selected to give desired yields and molar proportionsof the respective recurring units, y' and y are block lengths as definedabove, n is the total number of recurring units, and x is a molarquantity substantially less than m' that is selected to give anappropriate block length of the first homo-oligomer end-capped witho-diamine functional groups,

The preferred XIV block polymers are those wherein m', m, x, n, y, y'are as defined above, q is equal to m'/m+m' and p is equal to m/2(m+m').

Selected molar quantity, m, of a monomer of Type 1 may be mixed with aphosphoric acid having a phosphorus pentoxide content of from about 63%to about 78%, preferably greater than about 68%, most preferably about78%, and the protecting groups, if present, may be removed as describedpreviously. The quantity of the phosphoric acid is most desirablydetermined in accordance with equation a* as described above. Astoichiometric quantity (i.e., m) of a monomer of Type 2, 4, 6, 7, or 8may then be added to the resulting solution. The phosphorus pentoxidecontent of the resulting mixture may then be raised in accordance withequation b* given above, so as to raise the final phosphorus pentoxidecontent of the substantially polymerized mixture to a value greater thanabout 81%, most preferably between about 82% to about 83.5%, but lessthan about 84%. The resulting mixture may then be heated to about 100°C. to about 185° C., most preferably to about 170° C. to about 185° C.,within a practical period of time, preferably within a period of fromless than about one to about 5 hours, most preferably from about one toabout 3 hours. This temperature is maintained for sufficient time toachieve a selected n value, hereinafter referred to as thehomo-oligomeric n value, that is above a selected minimum value to bedescribed for specific cases below, is characterized as being equal to1/2(1-p), where p is the extent of reaction, defined as the molefraction of either type of functional group present that has undergonecondensation, and being preferrably below a selected maximum valuecharacteristic of complete polymerization. A selected molar quantity,m_(ij), of the homo-oligomeric reaction product thus obtained isdiverted into a second vessel containing a selected molar quantity,m_(ij), of a similarly obtained but structurally differenthomo-oligomeric reaction product and the heating at elevatedtemperatures continued.

The average block lengths, y_(ij), of the block polymers of thecompositions of the present invention may be determined in the followingway. The ijth homo-oligomeric reaction product is prepared by addinga_(i) moles of a first monomer to an equimolar b_(j) of the secondmonomer. The sum of all a_(i) or b_(j) is one. The ijth homo-oligomericreaction product prepared above has, by definition, been polymerized toa selected intermediate extent of reaction, P_(ij). The homo-oligomericn value of the ijth homo-oligomeric reaction product, n_(ij), is givenby 1/2(1-p_(ij)). The molar proportions of the recurring unitsincorporated into the block polymer is given by ##EQU5## The blocklengths y_(ij) may be calculated by the equation ##EQU6## which assumesthat the homo-oligomers condense with equal reactivity. The aboveequation for y_(ij) shows that if either of two homo-oligomeric reactionproducts are polymerized to high conversion, (i.e., allowed to achieve ahigh n_(ij) value before mixing) then both block lengths in theresulting block polymer will be high.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include block polymers withthe general formulas IX, XII, XVI, XVIII, and XIX is illustrated forthose compositions including general formula IX wherein the selectedfirst homo-oligomer may be prepared from monomers of Type 1 and Type 2that are further classified as belonging to Class 1 and the selectedsecond homo-oligomer is further characterized as belonging to eitherClass 1, Class 2, or Class 3.

General formula IX block polymers may be prepared from homo-oligomersderived exclusively from Class 1 monomers. The block polymers,##STR148## have the same advantage of a broad range of operableconcentrations as described for copolymers formed exclusively from Class1 monomers. The advantage to the block polymer procedure described abovefor these polymers is the ability to vary y₁₁ and y₁₂, or y₂₁, or y₂₂essentially independent of the molar proportion a₁ b₁, or a₂ b₂, or a₂b₁, or a₁ b₂ by selecting appropriate extents of reaction for thecorresponding homo-oligomer. For example, y₁₁ may be 20 or greater for abroad range of a₁ b₁ values by increasing the extent of reaction, p₁₁,as the a₁ b₁ value is decreased. y₁₂, y₂₁, or y₂₂ of the above formulasmay be obtained with values from about one to about 75, most preferablyfrom about 25 to about 50, by selecting appropriate p₁₁ and p₁₂, p₂₁, orp₂₂ values. In practice, the members of this selected class of blockpolymers, because all the recurring units have a high degree ofmesogenicity, are liquid-crystalline when an n value of greater thanabout 40 is obtained at a concentration of greater than about 6 weightpercent independent of the block lengths achieved. The practice of theinvention as it relates to block polymers of Class 1 is furtherillustrated in Examples 75-84 below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 2 monomers. The block polymers, ##STR149## arederived from homo-oligomers of different mesogenicity. The selection ofa₁ b₁ (the molar proportion of the first and more highly mesogenicrecurring unit) and the preferred y₁₁ (the average block length of thefirst and more highly mesogenic recurring unit) are governed by thefollowing considerations. The block polymer reaction product is thefirst case may derive liquid-crystalline behavior by virtue of the solepresence of the first recurring unit when y₁₁ is greater than about 30,more preferably greater than about 40, at concentrations of the firstrecurring unit alone (i.e., the weight of the first oligomeradded/weight of the final block polymer reaction product) greater thanabout 7 percent, or the block polymer reaction product in the secondcase may derive liquid-crystalline behavior by virtue of the combinedpresence of both recurring units, independent of y₁₁, at concentrationsabove which the moderately mesogenic recurring unit derived from thesecond homo-oligomer is liquid-crystalline alone. The preferred valuesof a₁ b₁ are from about 0.4 to about one, with y₁₁ ranging from about 80to about 20, respectively, as a₁ b₁ is varied from 0.4 to one. The mostpreferred concentrations of these block polymers is above about 15weight percent but may be lower as either the a₁ b₁ value or the y₁₁value or both values are increased. The preferred n value for thesecompositions is from about 50 to 150, most preferably greater than 100.Obtaining sufficient n values may be aided by the addition of the secondhomo-oligomeric reaction product before the phosphorus pentoxide contentis raised to the value necessary for polymerization (i.e., when p₁₂ orp₂₁ is zero and n₁₂ or n₂₁ =1/2) and then adding the appropriate amountof phosphorus pentoxide to raise the mixture to sufficient phosphoruspentoxide content. This procedure aids in mixing and is most preferredwhen the homo-oligomeric n value of the first homo-oligomer, n₁₁, islarge. The practice of the invention as it relates to the preparation ofblock polymers of Class 2 is further illustrated in Examples 85-88below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 3 monomers. The block polymers ##STR150## derivetheir liquid-crystalline behavior entirely from the presence of thefirst recurring unit, its average block length y₁₁, and itsconcentration alone in the total weight of the final block polymerreaction product. Thus, the values of a₁ b₁, y₁₁, and concentration mustmeet the conditions of the first case described for the block polymerscontaining Class 2 monomers. The method of the invention allows thepreparation of such highly concentrated mixtures of mesogenic units,i.e., reaction products substantially higher in polymer concentrationthan that required for liquid-crystalline behavior, that incorporationof significant amounts of non-mesogenic units is possible if the aboveconditions are met.

The preferred values of a₁ b₁ are from about 0.6 to about one. Thepreferred values of y₁₁ are from at least about 30 to about 100, morepreferably between about 50 to 100. The preferred values of y₁₂ or y₂₁are from about one to about 50. The preferred values of n are from about50 to 200 with the most preferred values being about 100 to 150. Thepreferred selected concentrations of the block polymer are above about15 weight percent, especially as the proportion of the non-mesogenicrecurring unit is increased. The practice of the invention as it relatesto production of block polymers containing Class 3 monomers is furtherillustrated in Examples 73, 74, 89-94 below.

The practice of the invention as it relates to the production of novelliquid-crystalline compositions that include block polymers with thegeneral formulas X, XV, XVII are illustrated for block polymers offormula X wherein the selected first homo-oligomer is prepared from Type(1,1) or (1,2) and Type (2,1) monomers and the selected secondhomo-oligomer is prepared from monomers of Type (3,2).

The general formulas X, XV, and XVII liquid crystalline block polymercompositions shown above are prepared according to the followingprocedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1e) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2e) then increasing the phosphorus pentoxide content of the mixtureresulting from step (1e) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(3e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1e) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomer of step (a) whichforms the first homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, the general formulas X, XV, and XVII liquid crystallineblock polymer compositions shown above may be also prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) mixing a selected amount of the solution of step (b) with a selectedamount of at least one of a selected first homo-oligomeric product so asto form a first oligomeric-first monomer reaction medium, said firsthomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1c) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2c) then increasing the phosporus pentoxide content of the mixtureresulting from step (1) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization.

(3c) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said firsthomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1c) which forms the first monomer mixture, be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a reaction medium of greaterphosphorus pentoxide content suitable for polymerization,

(e) causing polymerization of the first oligomer-monomer at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

General formula X block polymers may be derived from a firsthomo-oligomer of Class 1 and a second homo-oligomer of Type (3,2). Theblock polymers of general formula X are prepared by a procedureanalogous to the procedure described for general formula IX blockpolymers, except that the second homo-oligomer is prepared from a singlemonomer. ##STR151## have preferred molar proportion of the firstrecurring unit, a₁ b₁ m/m+m' of from about zero to about 0.5 when theconcentration selected to be above about 15 weight percent. When a₁ b₁m/m+m' is selected to be above about 0.5 but less than one then theoperable concentration range is extended to include concentration of 7%,more preferably 10 weight percent. At concentrations above about 15weight percent all selected values of y₁₁ and values of y₁ greater thanabout 5 give liquid-crystalline products, but n must be greater thanabout 50, preferably above about 100 to give desirable mechanicalproperties.

The practice of the invention as it relates to the block polymers ofthis Class is further illustrated in Examples 102-112 below

General formula X block polymer may be derived from a firsthomo-oligomer of Class 2 and a second homo-oligomer of Type (3,2). Theblock polymers ##STR152## are prepared from two homo-oligomers of Class2 which dictates the selection of concentrations greater than about 15'weight percent. The molar proportions of the various recurring units areselected based on desired mechanical properties or the maintenance ofsolubility in two recurring units of different solubilitycharacteristics. The preferred values of y₁ are those from about 5-50,more preferably greater than 30. The practice of the invention as itrelates to block polymers of this Class is further illustrated inExamples 113-115 below.

The practice of the invention is illustrated for general formula XI forblock polymers prepared from a single monomer of Type (3,2).

The general formula XI liquid crystalline block polymer compositionsshown above are prepared according to the following procedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), and(d) with the overall proviso that at least one of the selected monomerof step (a) which forms the second homo-oligomeric product be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The block polymers ##STR153## have preferred values of c₁ between 0.5and one, owing to the greater solubility and mesogenicity of the firstrecurring unit and preferred values of y₁ greater than about 25 but lessthan about 100, owing to the higher mesogenicity. Concentrations greaterthan about 15%, more preferably greater than about 18%, and mostpreferably 20%, are selected. Examples 98-101 below further illustratethe method of the present invention.

The method of the invention also relates to the preparation of blockpolymers by the condensation of co-oligomeric reaction products, insteadof the homo-oligomeric reaction products described in the aboveprocedures, however these will not be described here for the sake ofsimplicity.

Intrinsic Viscosity

Intrinsic viscosity is determined by extrapolation of η_(rel) -1/c and1n η_(rel) /c to zero concentration in methane sulfonic acid at 30° C.

Anisotropic Character of the Compositions

The extended chain polymer compositions of this invention are opticallyanisotropic, i.e., microscopic regions of a given extended chaincomposition are birefringent; a bulk extended chain composition sampledepolarizes plane-polarized light because the light transmissionproperties of the microscopic areas of the extended chain compositionvary with direction. This characteristic is associated with theexistence of at least part of the extended chain polymer compositions inthe liquid crystalline or mesomorphic state.

The extended chain polymer compositions of this invention that exhibitoptical anisotropy do so while the extended chain polymer compositionsare in the relaxed state. This is in contrast to conventional polymersolutions which may be caused to depolarize plane-polarized light whensubjected to appreciable shear.

The extended chain polymer concentration of the compositions of theinstant invention is above the "critical concentration point." The"critical concentration point" is routinely determined usingconventional concentration and viscosity measuring techniques (seeKwolek U.S. Pat. No. 3,671,542).

Another qualitative determination of the liquid crystalline character ofthese extended chain polymer compositions may be made with the nakedeye. These extended chain polymer compositions may appear turbid or hazyand yet contain no, or practically no undissolved solid. When theextended chain polymer compositions, seen under reflected ordinarylight, is disturbed by shaking or rolling the vessel containing theextended chain polymer compositions or by only slow stirring, there isproduced a characteristic, readily observed, satin-like sheen or glowwhich is observed even after the disturbance ceases, and which decreasesin intensity thereafter. This may be described as being a pearly oropalescent quality of the extended chain polymer compositions of thisinvention. Compositions which are disturbed as described above oftengive the appearance of having striations and/or graininess in thesurface. These visual effects are observed in the liquid crystallineextended chain polymer compositions of this invention. This may commonlybe referred to as "stir opalescence." Further details on qualitative andquantitative determinations of optical anisotropy are presented inKwolek U.S. Pat. No. 3,671,542.

Fiber Preparation

The liquid crystalline compositions may be formed into fibers of highquality by spinning them into suitable baths such as by wet and "airgap" spinning techniques, using spinnerets and other apparatusconstructed of materials resistant to the strong acids used. In"air-gap" spinning the spinneret is usually located in air or in aninert gaseous medium a short distance (e.g., 1 to 24 cm) above thesurface of a coagulating bath.

However, air-gaps suitable for use in the present invention may rangefrom less than about 1 cm to about 150 cm or longer, preferably fromabout 2 cm to about 300 cm, more preferably from about 10 cm to about200 cm, and most preferably from about 10 cm to about 100 cm.

In the present invention, the initial draw ratio is approximately fromabout 1:1 to about 50:1 and higher. Preferably, the initial draw ratiois from about 20:1 to about 80:1, especially preferably, from about 60:1to about 200:1, and, most preferably, from about 100:1 to about 150:1.

The term "draw ratio", as is well known, is a measure of the degree ofstretching during the orientation of the fibrous material. In thepresent invention, the initial draw ratio is a measure of the degree ofstretching of the filaments which occurs between the extrusion orificesand the exit from the coagulation bath. The initial draw ratio isdefined as exit velocity divided by jet speed.

The jet speed is the speed at which the extruded polymer exits anextrusion orifice. It is conveniently determined by dividing the totalpolymer extrusion velocity by the total surface area of the extrusionorifices.

The exit velocity is the speed at which the filaments leave thecoagulation bath. Although any means of measurement may be used, theexit velocity is conveniently determined by the surface speed of therolls which take up the filaments after their exit from the bath. Thus,the speed of the wash rolls is preferably measured for this purpose.

Spinning of polybenzimidazole fibers by one working of this generaltechnique is described in, e.g., Tan U.S. Pat. No. 4,263,245. A varietyof baths may be used to coagulate the extruded dope into fibers. Thebaths may be, e.g., water or methanol and the like, or a dilute solutionof a mineral acid (for example, phosphoric acid or sulfuric acid and thelike). Preferably, the temperature of a coagulation bath is roomtemperature or below.

It is desirable to completely remove the spinning solvent from fibersamples prepared from the liquid crystalline compositions of thisinvention. Water alone or aqueous alkaline solutions may be used forremoval of the residual acid. A convenient method is to spray thethreadline as it leaves the coagulating bath with an aqueous alkalinesolution (e.g., saturated sodium bicarbonate), remove the surface liquidfrom the threadline with a wiping device (e.g., a sponge) or a jet, washwith water and/or aqueous alkaline solutions to reduce the acid content,and wind up the fibers on bobbins. The fibers may be soaked in water fora period sufficient to remove the acid. The thoroughly washed fibers maybe dried on the bobbin in the area of temperatures of up to about 110°C. They can also be conveniently dried on heated rolls.

The liquid crystalline compositions are especially suitable forextruding. This and other methods of article frabication are fullydescribed in J. S. Robinson, "Spinning, Extruding, and Processing ofFibers"; Chemical Technology Review No. 159, Noyes Data Corp., 1980. Theabove cited patents and/or publications are incorporated herein byreference.

The fibers prepared from the polymers of this invention exhibit highvalues of tensile properties, especially in the as-extruded state, i.e.,without subsequent hot drawing or annealing. The tensile properties ofthese as-extruded fibers can be enhanced by subjecting the undrawnfibers to a heat treatment. Fiber tensile properties.

Filament properties are measured on fibers that are conditioned at 21degrees C. and 65% relative humidity (R.H.) for at least 16 hours unlessotherwise specified. Yarn properties are measured on yarn that areconditioned at 24 degrees C. and 55% R.H. for at least 16 hours. Allmeasurements are made in the fiber conditioning environment.

Tenacity (breaking tenacity) (T), elongation (breaking elongation( (E),and initial modulus (Mi) are obtained from breaking a single filament ora multifilament yarn on an Instron tester (Instron Engineering Corp.,Canton, Mass.).

Single filaments are broken with a gage length (distance between jaws)of 1.0 inch (2.54 cm.). The results on 3 filaments are averaged. Yarnsare given 3 turns per inch (2.54 cm.) twist (under 0.1 g.p.d. tension)and broken with a 10 inch (25.4 cm.) gage length. All samples areelongated at a constant rate of extension (10% elongation/minute forfibers having an E of under 8%, and 60% elongation/minute for fiberswith E of 8 to 100%) until the sample breaks.

The denier of a single filament (d.p.f.) is calculated from itsfunctional resonant frequency, determined by vibrating a 7 to 9 cm.length of fiber under tension with changing frequency (ASTM D1577-1973).This filament is then used for 1 break.

The denier of yarn is determined by weighing a known length (at 0.1g.p.d. tension); 90 cm. length is convenient.

The tenacity (grams/denier), elongation (percent) and initial modulus(gram/denier) as defined in ASTM 3379-75e are obtained from theload-elongation curve and the measured denier. In actual practice, themeasured denier of the sample, test conditions and sample identificationmaybe fed to a computer before the start of a test; the computer recordthe load-elongation curve of the fiber as it is broken and thencalculates the fiber properties.

It should be noted that different values maybe obtained from singlefilaments (filament properties) and from multifilament strands (yarnproperties) of the same sample. Unless specified otherwise allproperties given herein are filament properties.

Additives

It will be understood that the usual additives such as dyes, fillers,antioxidants, and the like can be incorporated into the compositions ofthe present invention for the purpose intended, before preparation ofthe shaped article.

Mineral acids that are solvents for the extended chain polymers of theinstant compositions such as polyphosphoric acid, methane sulfonic acid,100% sulfuric acid, chlorosulfonic acid, and the like, may be added tothe compositions of the invention in minor amounts (without departingfrom the scope of the invention) for purposes of modifying conditionsfor processing into shaped articles. The strong acid additives maycontain one or more of the acid-soluble polymers described in Helmimiak,et. al., U.S. Pat. No. 4,207,407 and P. D. Sybert, "Rigid-RodPolyquinolines: Synthesis, Structure-Property Relationships andHigh-Strength Fibers", Colorado State University, Ph.D. Thesis, 1980.The above cited patent and thesis are incorporated herein by reference.4. Industrial Applicability

The liquid crystalline extended chain polymer compositions are extremelysuitable for spinning into highly ordered and high strength fibers. Suchfibers are useful as reinforcement substitutes for other inorganic ororganic products. Various examples include glass fibers, asbestos, boronfibers, carbon and graphite fibers, whiskers, quartz and silica fibers,ceramic fibers, metal fibers, natural organic fibers, and syntheticorganic fibers. A reinforcement may be defined simply as the materialthat is added to a resinous matrix to improve the strength and otherphysical and chemical properties of the material.

Furthermore, the polymers of the instant compositions can be employed inany use typically performed by engineering thermoplastic materials, suchas metal replacements and those areas where high performance isnecessary. Extended chain polymer compositions may be employed for usein forming high strength films suitable in the production of composites,belts, tires, i.e., as tire cords, and the like. The films are suitableas construction materials for rocket nose cones and various other partsof space craft.

Depending on the extended chain polymer fiber or films selected (i.e.,homopolymer, copolymer, block polymer, or mixture thereof) theproperties of the article formed may be controlled to suit the desireduse. The control of polymer properties is an advantage, since, in thevarious areas of utility for such polymers, e.g. as laminates,structural materials, adhesives and ablative materials, the needs varyconsiderably.

By way of comparison, Examples 1-5 below are illustrative of lowmolecular weight (i.e., low intrinsic viscosity) and/or low polymerconcentration compositions.

EXAMPLE 1

In a 6-L resin flask were placed 386.76 g (1.5774 mol) of2,5-diamino-1,4-benzenedithiol dihydrochloride (1a) and 2.98 kg offreshly prepared PPA. The PPA was prepared as described in Wolfe andArnold, Macromolecules, Vol 14, 909 (1981). The mixture was stirred atroom temperature under a flow of argon for 24h and heated at 60°-70° C.for 34h. The resulting solution was clear with no evidence of bubbles.Terephthalic acid (262.35 g, 1,5792 mol) was then added and incorporatedinto the solution by rapid stirring at 110° C. Additional PPA (4.1 kg)was then added. The yellow mixture was heated as follows: 110°-165° C.in 5h, 165° C. for 12h, 180° C. for 12h, and 195° C. for 12h. Themixture became stir-opalescent after 6h at polymerization temperatures.Reduced pressure was applied during the first 6h of reaction but wasalternated with an argon stream such that the mixture did not foam abovea predetermined flask wall level. The hazy green product exhibitingyellow-green opalescence was removed from the flask and precipitatedinto a large volume of water. The copper-colored polymer was washeduntil the water was no longer acidic and then dried at 80°-100° C. underreduced pressure for 48h. A portion of the reaction product was bottledfor use in fiber-spinning studies: intrinsic viscosity [η]=30.3 dL/g(MSA). Anal.Calcd for C₁₄ H₆ N₂ S₂ : C,63.13; H,2.27; N,10.51; S,24.08.Found: C,62.75; H, 2.346; N, 10.24; S, 23.22. The foregoing procedureprovided a 5.6 wt % of polymer --AI]_(n) in PPA. Polymerization mixturesof higher polymer concentration (up to 10%) were prepared. These runsrequired higher monomer 1a concentration during dehydrochlorination.Intermittent cooling was cycled with argon pressure as required tocontrol foaming at the desired level in the reaction vessel. Similarly,polymer --AI]_(n) in PPA of lower concentration were prepared and theserequired less time for complete dehydrochlorination than that described.

EXAMPLE 2

In a 6-L resin flask were placed 919.94 g (3.7519 mol) of 1a andapproximately 2.7 kg of 115% PPA; the % P₂ O₅ content profile for thisExample is illustrated in FIG. 8. The 115% PPA was obtained from FMCCorporation and heated to 150° C. under an argon atmosphere, heated at150° C. under reduced pressure for 18h, and cooled to room temperatureimmediately before use. The viscous mixture was stirred and an ice bathwas applied for 24h to prevent vigorous foaming. Five additional days ofstirring at room temperature were required to remove enough hydrogenchloride to allow heating above room temperature. A clear, viscoussolution was obtained after heating for 18h at 80° C. Finely powdered 2a(622.90 g, 3.7454 mol) and an additional 2.773 g of the above 115% PPAwere then added. The mixture was then stirred and heated to 140° C. for3h and then heated at 150°-160° C. for 16h. The mixture graduallydarkened, became optically isotropic, and never became noticeably moreviscous. Samples that were removed and precipitated in water gave a darkgreen non-fibrous material. Additional heating failed to increase theviscosity to an extent to yield a fibrous material. The theoreticalpolymer concentration --AI] for this experiment was 14.8% in a PPA withan intermediate P₂ O₅ content of 83.8% and a final of 79.8%.

EXAMPLE 3

To a 100 mL flask containing 15.8 g of concentrated orthophosphoric acid(85.4% H₃ PO₄) that had been cooled in an ice bath was added 24.2 g ofphosphorus pentoxide and the mixture heated at 150° C. for 6h under anargon atmosphere. The % P₂ O₅ content profile for this Example isillustrated in FIG. 9. After cooling the PPA (84.9% P₂ O₅) to roomtemperature, 6.0 g (0.029 mol) of 4-amino-3-mercaptobenzoic acidhydrochloride (3a) (prepared by the method of Wolfe, AFOSR FinalTechnical Report, Dec. 15, 1980) was added and the viscous mixturestirred at 40° C. for 24h. The mixture was then placed under reducedpressure and the temperature slowly raised to 70° C. The orangeyellowmixture was then heated to 150° C. over a 2h period. The resulting darkred solution was optically isotropic. The solution was then stirred at150° C. for an additional 24h. The polymer was isolated from theresulting optically isotropic solution containing 8.6% of the polymer byprecipitation with water to give brittle films. The intrinsic viscosityof the isolated polymer --T]_(n) was 3.0 dL/g in methanesulfonic acid at30° C.

EXAMPLE 4

To a 50 mL round bottom flask containing 48.15 g of PPA that wasprepared as described in Wolfe and Arnold, Macromolecules, Vol. 14, 909(1981) was added 7.436 g (0.03616 mol) of 4-amino-3-mercaptobenzoic acidhydrochloride (3a) that was prepared as described in Wolfe, AFOSR FinalTechnical Report, Dec. 15, 1980. The mixture was stirred at roomtemperature under an argon flow for 18h. After stirring for 2h underreduced pressure between 50° to 80° C. the solution was a clear orangecolor. The solution was then heated under reduced pressure as follows:90° C. for 0.5h; 100° C. for 0.5h; 110° C. for 0.5h; 130° C. for 0.5h;140° C. for 0.5h; 180° C. for 8h; 150° C. for 5h; 190° C. for 16h; 160°C. for 16h; 160° C. for 16h; 200° C. for 200h and 170° C. for 7h. Theresulting isotropic solution havinga concentration of polymer --T]_(n)of 9.4% by weight gave only brittle amorphous films when precipitated inwater. The intrinsic viscosity of the isolated polymer was 3.80 dL/g inmethanesulfonic acid at 30.0° C.

EXAMPLE 5

To 38 g of PPA that was prepared as de scribed in Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981) was added 1.421 g (8.41 mmol) of4-amino-3-mercaptobenzoic acid (3b) that was prepared by neutralizationof an aqueous suspension of 4-amino-3-mercaptobenzoic acid hydrochloride(3a) (prepared according to Wolfe, AFOSR Final Technical Report, Dec.15, 1980) followed by extraction with ethyl acetate, evaporation of theethyl acetate, and recrystallization of the pale yellow residue frommethylene chloride. The viscous mixture was heated to 140° C. under anargon flow in a 0.5h period. The temperature was raised to 160° C. overa 0.5h period and then maintained at 160° C. for 18h under reducedpressure. The optically isotropic, red solution was then heated underreduced pressure for 8h at 200° C. The isolated polymer --T]_(n) had anintrinsic viscosity of 4.57 dL/g in MSA at 30.0° C.

The compositions of this invention, their production and theiradvantages and uses are further illustrated in the following examples.These are intended only to demonstrate the invention and are not to beconstrued as limiting its scope, which scope is instead defined by theappended claims.

All polyphosphoric acid (PPA) hereinafter referred to as 115% wasobtained from FMC Corporation and used as received. Terephthalic acid(2a) was obtained from Amoco Chemicals Company, reduced to an averageparticle size of 95% <10 μm by an air-impact method, and dried beforeuse. All monomers and P₂ O₅ that were added to PPA were deaerated byplacing them in a desiccator, applying reduced pressure, filling with aninert gas, and repeating the procedure at least once.

EXAMPLE 6

A mixture of 88.2 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 205.2 g of 115% PPA was stirred at 100° C. for 2h under reducedpressure. After allowing the PPA solution to cool to approximately 50°C. a portion of this solution (282.1 g) was added to a 500 mL resinkettle containing 53.01013 g (0.21620 mol) of 1a. After stirring toincorporate the solid monomer into the PPA, the mixture was stirred atroom temperature for 2h under argon and then under reduced pressure at:25°-30° C. for 24h; 50° C. for 3h; and 70° C. for 16h. Monomer 2a(35.91734 g, 0.216196 mol) was then added to the resulting clear lightgreen soltion in four portions. After the addition of each portion, thereaction kettle was placed under reduced pressure before the 2a wasincorporated by stirring. The mixture was allowed to cool toapproximately 50° C. before 118.3 g of P₂ O₅ was added to increase theeffective P₂ O₅ content to 83.9%. The viscous slurry was then heated asfollows: 100°-170° C. in 3h; 170° C. for 17h; 185° C. for 5h; and 200°C. for 19h. The intrinsic viscosities (in dL/g) of the polymer --AI]_(n)were determined from samples of the polymer solution withdrawn at thepolymerization times indicated: 9.2 (8.5h), 12.6 (25.5h), 15.8 (44.0h).Heating this reaction solution at 200° C. for an additional 76h onlyincreased the intrinsic viscosity of the --AI]_(n) component to 16.4dL/g. The reaction product is characterized as having a final P₂ O₅content of approximately 80.8% with the --AI]_(n) polymer concentrationbeing approximately 12.6 wt %.

EXAMPLE 7

A mixture of 57.3 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 133.7 g of 115% PPA was stirred at 100° C. for 4h under reducedpressure. After allowing the PPA solution to cool to room temperature, aportion of this solution (185.0 g) was added to a 500 mL resin kettlecontaining 53.61422 g (0.21866 mol) of 1a. (Monomer 1a of small crystalsize was prepared without a final recrystallization according to themethod of Wolfe, Loo, and Arnold, Macromolecules Vol. 14, 915 (1981)using the final isolation procedure involving the transfer of thedipotassium salt of 1a as an aqueous solution into 6N hydrochloricacid.) After stirring to incorporate the monomer into the PPA, themixture was stirred at 55°-65° C. for 5.5h under reduced pressure, at25° C. for 15.5h under an argon flow, and at 65°-72° C. for 4h underreduced pressure. Monomer 2a (36.3268 g), 0.21866 mol) was added to theresin kettle cotaining the dehydrochlorinated solution of monomer 1a inPPA. After the addition of each of the six portions, the incorporationof the solid into the solution was aided by placing the kettle underreduced pressure before stirring was initiated. Powdered phosphoruspentoxide (114.4 g) was then added to increase the effective P₂ O₅content to 86.4% and the mixture was stirred at 100° C. for 27h. Thepolymerization mixture was then heated as follows: 100°-170° C. in 1h;170° C. for 21.5h; and 200° C. for 71.5h. The intrinsic viscosities (indL/g) of the polymer --AL]_(n) were determined from samples withdrawn atthe polymerization times indicated: 23.1 (22.5h), 24.8 (29.0h), 27.0(94h). The reaction product is characterized as having a final effectiveP₂ O₅ content of approximately 82.2% and a polymer --AI]_(n)concentration being approximately 15.2 wt %.

EXAMPLE 8

182.7 g of a PPA solution with an effective P₂ O₅ content of 77.2%(prepared by mixing 30 wt % of H₃ PO₄ and 70 wt % of 115% PPA) was addedto a 500 mL resin kettle containing 52.62853 g (0.21460 mol) of 1a.(Monomer 1a of large crystal size was prepared with a finalrecrystallization according to the method of Wolfe, Loo, and Arnold,Macromolecules, 14, 915 (1981) using the final isolation procedureinvolving a transfer of the dipotassium salt of monomer 1a as solid into6N hydrochloric acid.) After stirring to incorporate the solid monomerinto the PPA, the mixture was substantially dehydrochlorinated byheating the mixture at 55°-70° C. under reduced pressure forapproximately 31h. Monomer 2a (35.6522 g, 0.21460 mol) was added to theresin kettle and incorporated as described in the previous Example.Powdered P₂ O₅ (123.35 g) was then added to increase the effective P₂ O₅content to approximately 86.4% and resulting mixture was stirred at 100°C. for 17h under an argon flow. The polymerization mixture was thenheated with stirring as follows: 100°-170° C. in 1h, 170° C. for 23h,and 200° C. for 24h. The intrinsic viscosities (in dL/g) were determinedfor the --AI]_(n) polymer from samples withdrawn at the indicated times:17.2 (7h), 22.8 (24h), and 35.4 (48h). Heating without stirring for anadditional 24h did not increase the intrinsic viscosity of the --AI]_(n)polymer. The green reaction product exhibits stir-opalescence and ischaracterized as having a final effective P₂ O₅ content of 82.2% with--AI]_(n) polymer concentration being approximately 15.1 wt %.

EXAMPLE 9

A mixture of 4,925 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 11.491 g of 115% PPA was stirred in a 22 L flask for 5h at 100° C.under reduced pressure. After allowing the PPA solution to cool to 50°C. under a flow of argon, a portion of this solution (11,321 g) wasadded to a 40-L glass resin kettle (equipped with a mechanical stirrerconsisting of a 3/4 hp variable speed drive and stirring blades made ofHastelloy C-276) containing 2,380.55 g (9.7088 mol) of 1a prepared asdescribed in Example 7. The mixture was then stirred at: 65° C. for 17hunder a flow of argon; 65° C. for 2h at 700-400 mm Hg; and 65° C. for 2hat 40 mm Hg. An additional 2,552.77 g (10.4112 mol) of monomer 1a thathad been prepared and deaerated as described in Example 8 was then addedunder a flow of argon. An additional 4,874 g of the above-mentioned PPAwas added and the mixture stirred at: 65° C. for 1h at 700-300 mm Hg;65°-70° C. for 3.25h at 40 mm Hg; 70° C. for 2.5h at less than 5 mm Hg;700° C. for 7.5h under a flow of argon; and 80° C. for 26h at less than5 mm Hg. Monomer 2a (3,342.62 g, 20.1205 mol) was then added. Theresulting slurry was then cooled to 40° C. and 6,512.1 g of powdered P₂O₅ was added over a 4.5 period. The resulting viscous mixture wasstirred at 80° C. for 17h under an argon flow. The mixture was thenheated to 100° C. and an additional 4,655.4 g of P₂ O₅ was added toincrease the effective P₂ O.sub. 5 content to 86.5%. After stirring foran additional 48h at 100°-108° C., the polymerization mixture was heatedas follows: 100°-170° C. in 3h; 170° C. for 20h; and 200° C. for 1.5h.The intrinsic viscosities (in dL/g) were determined from sampleswithdrawn at the indicated reaction times: 17.9 (14h), 18.5 (16.5h),19.0 (23h), 24.34 (24.5h). Additional heating at 200° C. only increasedthe intrinsic viscosity to 24.6 dL/g. The reaction product exhibitedstir-opalescence and is characterized as having a final effective P₂ O₅content of 82.2% with the --AI]_(n) polymer concentration beingapproximately 15.6% by weight.

EXAMPLE 10

To a 500 mL resin kettle containing a deaerated mixture of 12.06155 g(0.0594092 mol) of terephthaloyl chloride (2b) and 14.5665 g (0.0594081mol) of 1a was added approximately 140 g of 115% PPA that had beenstirred at 100° C. under reduced pressure for 1-2h, and had cooled toroom temperature. The mixture was then stirred under an argon flow at:40° C. for 23h; 50° C. for 3h; 60° C. for 2h; 70° C. for 19h; and 80° C.for 3h. The solution was then stirred at 80° C. under reduced pressurefor 1h. An additional 140 g of deaerated 115% PPA was then incorporatedinto the solution. The polymerization was stirred under argon at: 100°C. for 30 min; 110° C. for 30 min; 120° C. for 30 min; 130° C. for 30min; 140° C. for 30 min; 150° C. for 30 min; 160° C. for 45 min; 170° C.for 11h; 185° C. for 5h; and 200° C. for 46.5h. Precipitation in waterof a small amount of the anisotropic product provided polymer --AI]_(n)which possessed an intrinsic viscosity of 17.7 (dL/g) in MSA at 30° C.

EXAMPLE 11

A mixture of 74.52 g of 85.7% orthophosphoric acid and 173.88 g of 115%PPA (83.8% P₂ O₅ content) is stirred under reduced pressure for 2h at100° C. After cooling to room temperature, 55.23561 g (0.225273 mol) of1a (prepared as described in Example 8) and 45.73607 g (0.225273 mol) of2b (freshly sublimed) are added in eight portions. After the addition ofeach portion of monomer stirring is initiated to incorporate themonomer. The mixture is then stirred while the temperature is slowlyincreased and the pressure is slowly decreased until dehydrochlorinationis complete. Deaerated phosphorus pentoxide (87.54 g) is then added tothe dehydrochlorination mixture at 50° C. The mixture is then stirred at100° C. for several hours. The polymerization is then stirred under anargon atmosphere at 170° C. for approximately 20h, at 180° C. forapproximately 8h, and at 200° C. for 3h. The resulting product contains15 wt % of --AI]_(n) in PPA (82.2% P₂ O₅).

EXAMPLE 12

86.17 g of a PPA solution with an effective P₂ O₅ content of 74.9%(prepared by mixing 40 wt % of 85% H₃ PO₄ and 60 wt % of 115% PPA) wasadded to a 500 mL resin kettle containing 27.62485 g (0.112665 mol) of1a. The monomer was incorporated into the PPA solution by stirring andthe resulting mixture was then substantially dehydrochlorinated byheating the mixture at 55°-80° C. under reduced pressure forapproximately 21hours. The % P₂ O₅ content profile for this Example isillustrated in FIG. 10. Monomer 2a (18.7208g, 0.112686 mol) was thenadded to the resin kettle. Powdered P₂ O₅ (83.17 g) was then added toincrease the effective P₂ O₅ content to approximately 87.2%. Theresulting yellow slurry was stirred at 100° C. for 15h under an argonflow. This slurry, which had not noticeably increased in bulk viscosity,was then stirred vigorously and heated by increasing the oil bathtemperature from 100° C. to 178° C. within 40 minutes, and to 185° C.within 1h. Polymerization times indicated below begin with time above100° C. The 185° C. temperature was then maintained for 76.5h. Intrinsicviscosities in MSA at 30° C. (in dL/g) were determined for the --AI]_(n)polymer from samples withdrawn at the indicated polymerization times:16.6 (1.5h), 21.7 (2.25h), 24.2 (3.25h), 35.7 (7.7h), and 42.1 (76.5h).The intrinsic viscosity of 42.1 corresponds to an average n value ofpolymerization of about 140. The polymerization product wasstir-opalescent after a polymerization time of 0.75h and was found to behighly drawable after 1.25h. Fibers prepared by directly drawing thisproduct and precipitating the strands into water were amber,translucent, birefringent (crossed polars), showed extinction oftransmitted light when a single polaroid sheet was placed perpendicularto the fiber direction, and could be fibrillated into microfibrils.Fibers prepared after 1.5h by the same method were noticeably strongerthan the sample at 1.25h. The bulk viscosity of the product and therelaxation time of opalescence had noticeably increased after 2.25h. TheP₂ O₅ content of the PPA component of the product was approximately83.2% and the concentration of the --AI]_(n) polymer was 14.5% by weightbased on the total weight of the resulting reaction product.

EXAMPLE 13

A mixture of 17.7 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 26.6 g of 115% PPA was stirred under reduced pressure at 100° C. for2hours. The % P₂ O₅ content profile for this Example is illustrated inFIG. 11. The resulting solution was then poured at approximately 100° C.under a stream of argon into a 200 mL resin kettle containing 11.41145 g(0.054028 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981), recrystallized from aqueoushydrochloric acid containing 3 wt % stannous chloride, and dried for 20hat 63° C. under reduced pressure immediately before use. The mixture wasstirred at 53° C. for 15h and 62° C. for 4h under reduced pressure. Uponheating to 70° C., the monomer precipitated. Addition of 16.6 g of P₂ O₅resulted in redissolution of the monomer. The solution was then heatedat 100° C. for 3h under reduced pressure to complete thedehydrochlorination. Monomer 2a (8.9761 g, 0.05403 mol) was then addedunder an argon flow. Additional P₂ O₅ (19.0 g) was then added. Thesolution was then heated as follows: 100° C. for 48h; 150° C. for 2.5h;160° C. for 10h (the dark green solution became stiropalescent duringthis period); and 180° C. for 25h. The resulting reaction product wasdeep purple with a metallic luster, exhibited stiropalescence,depolarized plane-polarized light as evidenced by strong birefringencewhen viewed between crossed polars, and is further characterized ashavng a final effective P₂ O₅ content of 82% with the --BI]_(n) polymerconcentration being 13.3% by weight. The intrinsic viscosity of thepolymer --BI]_(n) isolated from the reaction product was 23.9 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 110.

EXAMPLE 14

The reaction product from Example 13 was drawn many times its length togive highly fibrillar fibers. A portion of the solution was removed fromthe reaction flask and placed in a KBr press equipped with a die with acircular orifice of 0.13 mm in diameter. The solution was extruded intothe air and stretched by pulling manually and then the fiber was dippedin water. The fiber thus produced was washed with water and then driedunder tension in an air oven overnight at 110° C. The fiber produced wasmeasured to be between 0.0093 mm and 0.012 mm in diameter. Highorientation was evident from fibrils which split from the surface of thefiber and by the complete extinction of light transmitted through thefiber when a single polaroid was placed in a perpendicular directiononly between the source and the fiber.

EXAMPLE 15

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 48.9831 g (0.19978 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 269.68 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 80.9 g of 85.4% H₃ PO₄ with 188.8 g of 115% PPA).When dehydrochlorination is substantially complete, 79.9805 g (0.19978mol) of monomer 2s is added followed by the gradual addition of 142.23 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 85.07%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 19%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AIBI].sub.n

characterized by an intrinsic viscosity of 20 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 50.

EXAMPLE 16

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 64.4470 g (0.26284 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 341.97 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 102.6 g of 85.4% H₃ PO₄ with 239.4 g of 115% PPA).When dehydrochlorination is substantially complete, 63.6826 g (0.26284mol) of monomer 2j is added followed by the gradual addition of 137.3 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --A].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 100.

EXAMPLE 17

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 61.1619 g (0.28706 mol) of monomer 1b is dehydrochlorinatedin an "initial" solution of 338.4 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 101.5 g of 85.4% H₃ PO₄ with 236.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.5488 g (0.28706mol) of monomer 2j is added followed by the gradual addition of 140.1 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AB].sub.n

characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization fo about 60.

EXAMPLE 18 64

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 81.9923 g (0.28869 mol) of monomer 1c is dehydrochlorinatedin an "initial" solution of 366.8 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 110 g of 85.4% H₃ PO₄ with 256.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.9438 g (0.28869mol) of monomer 2j is added followed by the gradual addition of 148.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 16%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AC].sub.n

characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 60.

EXAMPLE 19

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.8232 g (0.29202 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 263.5 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 79.1 g of 85.4% H₃ PO₄ with 184.4 g of 115% PPA).When dehydrochlorination is substantially complete, 48.5129 g (0.29202mol) of monomer 2a is added followed by the gradual addition of 171 g ofP₂ O₅. The mixture is then stirred and heated essentially according toExample 8. The amount of P₂ O₅ is preselected (as determined in accordwith the aforementioned formulae a* and b*) to provide the reactionmixture with an effective P₂ O₅ content of approximately 86.2% prior tothe start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --LI].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 20

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 254.0 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 76.2 g of 85.4% H₃ PO₄ with 177.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added, followed by the gradual addition of 178.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --MI].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 21

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 254.0 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 76.2 g of 85.4% H₃ PO₄ with 177.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added, followed by the gradual addition of 178.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --NI].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 22

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 128.4748 g (0.32431 mol) of monomer 1l is dehydrochlorinatedin an "initial" solution of 233.5 g PPA having a P₂ O₅ content of 79.4%(prepared by mixing 44.7 g of 85.4% H₃ PO₄ with 178.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.8778 g (0.32431mol) of monomer 2a is added, followed by the gradual addition of 197.0 gof P₂ O₅. Inorganic salts, such as lithium salts (e.g., LiCl, LiF,Lithium phosphate, and the like) can be added at this point, ifrequired, to promote polymer solubility. The mixture is then stirred andheated essentially according to Example 8. The amount of P₂ O₅ ispreselected (as determined in accord with the aforementioned formulae a*and b*) to provide the reaction mixture with an effective P₂ O₅ contentof approximately 89.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent tosubstantially complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 18%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --OI].sub.n

characterized by an intrinsic viscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 23

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.3707 g (0.21902 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 323.1 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.9 g of 85.4% H₃ PO₄ with 226.2 g of 115% PPA).When dehydrochlorination is substantially complete, 53.0654 g (0.21902mol) of monomer 2j is added followed by the gradual addition of 125.0 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AL].sub.n

characterized by an intrinsic viscosity of 17 dL/g in MSA at 30° C.

EXAMPLE 24

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 320.7 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.2 g of 85.4% H₃ PO₄ with 224.5 g of 115% PPA.When dehydrochlorination is substantially complete, 57.824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 126.9 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AM].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 25

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 320.64 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.19 g of 85.4% H₃ PO₄ with 184.4 g of 115% PPA).When dehydrochlorination is substantially complete, 57.0824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 126.88 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --AN].sub.n

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 6-25, other Type I extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 16a, 16b,17a, 17b, and 17c. The m→, e→, and p→ denote most preferred, especiallypreferred, and preferred selected monomer reactions respectively.

                  TABLE 16a                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR154##                                                                    ##STR155##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR156##                                                                           Polymer I(1)                              ______________________________________                                        1a        +     2e                                                                                         ##STR157##                                                                          [AJ].sub.n                                 1a        +     2f                                                                                         ##STR158##                                                                          [AJ].sub.n                                 1a        +     2i                                                                                         ##STR159##                                                                          [AK].sub.n                                 1a        +     2k                                                                                         ##STR160##                                                                          [AB].sub.n                                 1a        +     2l                                                                                         ##STR161##                                                                          [AC].sub.n                                 1a        +     2m                                                                                         ##STR162##                                                                          [AD].sub.n                                 1a        +     2n                                                                                         ##STR163##                                                                          [AE].sub.n                                 1a        +     2o                                                                                         ##STR164##                                                                          [AF].sub.n                                 1a        +     2p                                                                                         ##STR165##                                                                          [AG].sub.n                                 1a        +     2q                                                                                         ##STR166##                                                                          [AH].sub.n                                 1a        +     2t                                                                                         ##STR167##                                                                          [AICI].sub.n                               1a        +     2u                                                                                         ##STR168##                                                                          [AIDI].sub.n                               1a        +     2v                                                                                         ##STR169##                                                                          [AIEI].sub.n                               1a        +     2w                                                                                         ##STR170##                                                                          [AIFI].sub.n                               1a        +     2x                                                                                         ##STR171##                                                                          [AIGI].sub.n                               1a        +     2y                                                                                         ##STR172##                                                                          [AIHI].sub.n                               1b        +     2e                                                                                         ##STR173##                                                                          [BJ].sub.n                                 1b        +     2i                                                                                         ##STR174##                                                                          [BK].sub.n                                 1b        +     2k                                                                                         ##STR175##                                                                          [B].sub.n                                  1b        +     2l                                                                                         ##STR176##                                                                          [BC].sub.n                                 1b        +     2m                                                                                         ##STR177##                                                                          [BD].sub.n                                 1b        +     2n                                                                                         ##STR178##                                                                          [BE].sub.n                                 1b        +     2o                                                                                         ##STR179##                                                                          [BF].sub.n                                 1b        +     2p                                                                                         ##STR180##                                                                          [BG].sub.n                                 1b        +     2q                                                                                         ##STR181##                                                                          [BH].sub.n                                 1b        +     2t                                                                                         ##STR182##                                                                          [BICI].sub.n                               1b        +     2u                                                                                         ##STR183##                                                                          [BIDI] .sub.n                              1b        +     2v                                                                                         ##STR184##                                                                          [BIEI].sub.n                               1b        +     2w                                                                                         ##STR185##                                                                          [BIFI].sub.n                               1b        +     2x                                                                                         ##STR186##                                                                          [BIGI].sub.n                               1b        +     2y                                                                                         ##STR187##                                                                          [BIHI].sub.n                               1c        +     2a                                                                                         ##STR188##                                                                          [CI].sub.n                                 1c        +     2e                                                                                         ##STR189##                                                                          [CJ].sub.n                                 1c        +     2i                                                                                         ##STR190##                                                                          [CK].sub.n                                 1c        +     2k                                                                                         ##STR191##                                                                          [BC].sub.n                                 1c        +     2l                                                                                         ##STR192##                                                                          [C].sub.n                                  1c        +     2m                                                                                         ##STR193##                                                                          [CD].sub.n                                 1c        +     2n                                                                                         ##STR194##                                                                          [CE].sub.n                                 1c        +     2o                                                                                         ##STR195##                                                                          [CF].sub.n                                 1c        +     2p                                                                                         ##STR196##                                                                          [CG].sub.n                                 1c        +     2q                                                                                         ##STR197##                                                                          [CH].sub.n                                 1c        +     2u                                                                                         ##STR198##                                                                          [CIDI].sub.n                               1c        +     2v                                                                                         ##STR199##                                                                          [CIEI].sub.n                               1c        +     2w                                                                                         ##STR200##                                                                          [CIFI].sub.n                               1c        +     2x                                                                                         ##STR201##                                                                          [CIGI].sub.n                               1c        +     2y                                                                                         ##STR202##                                                                          [CIHI].sub.n                               1d        +     2a                                                                                         ##STR203##                                                                          [DI].sub.n                                 1d        +     2e                                                                                         ##STR204##                                                                          [DJ].sub.n                                 1d        +     2i                                                                                         ##STR205##                                                                          [DK].sub.n                                 1d        +     2m                                                                                         ##STR206##                                                                          [D].sub.n                                  1d        +     2n                                                                                         ##STR207##                                                                          [DE].sub.n                                 1d        +     2o                                                                                         ##STR208##                                                                          [DF].sub.n                                 1d        +     2p                                                                                         ##STR209##                                                                          [DG].sub.n                                 1d        +     2q                                                                                         ##STR210##                                                                          [DH].sub.n                                 1d        +     2v                                                                                         ##STR211##                                                                          [DIEI].sub.n                               1d        +     2w                                                                                         ##STR212##                                                                          [DIFI].sub.n                               1d        +     2x                                                                                         ##STR213##                                                                          [DIGI].sub.n                               1d        +     2y                                                                                         ##STR214##                                                                          [DIHI].sub.n                               1e        +     2a                                                                                         ##STR215##                                                                          [EI].sub.n                                 1e        +     2e                                                                                         ##STR216##                                                                          [EJ].sub.n                                 1e        +     2i                                                                                         ##STR217##                                                                          [EK].sub.n                                 1e        +     2n                                                                                         ##STR218##                                                                          [E].sub.n                                  1e        +     2o                                                                                         ##STR219##                                                                          [EF].sub.n                                 1e        +     2p                                                                                         ##STR220##                                                                          [EG].sub.n                                 1e        +     2q                                                                                         ##STR221##                                                                          [EH].sub.n                                 1e        +     2w                                                                                         ##STR222##                                                                          [EIFI].sub.n                               1e        +     2x                                                                                         ##STR223##                                                                          [EIGI].sub.n                               1e        +     2y                                                                                         ##STR224##                                                                          [EIHI].sub.n                               1f        +     2a                                                                                         ##STR225##                                                                          [FI].sub.n                                 1f        +     2e                                                                                         ##STR226##                                                                          [FJ].sub.n                                 1f        +     2i                                                                                         ##STR227##                                                                          [FK].sub.n                                 1f        +     2o                                                                                         ##STR228##                                                                          [F].sub.n                                  1f        +     2p                                                                                         ##STR229##                                                                          [FG].sub.n                                 1f        +     2q                                                                                         ##STR230##                                                                          [FH].sub. n                                1f        +     2x                                                                                         ##STR231##                                                                          [FIGI].sub.n                               1f        +     2y                                                                                         ##STR232##                                                                          [FIHI].sub.n                               1g        +     2g                                                                                         ##STR233##                                                                          [GI].sub.n                                 1g        +     2e                                                                                         ##STR234##                                                                          [GJ].sub.n                                 1g        +     2i                                                                                         ##STR235##                                                                          [GK].sub.n                                 1g        +     2p                                                                                         ##STR236##                                                                          [G].sub.n                                  1g        +     2q                                                                                         ##STR237##                                                                          [GH].sub.n                                 1g        +     2y                                                                                         ##STR238##                                                                          [GIHI].sub.n                               1h        +     2a                                                                                         ##STR239##                                                                          [HI].sub.n                                 1h        +     2e                                                                                         ##STR240##                                                                          [HJ].sub.n                                 1h        +     2i                                                                                         ##STR241##                                                                          [HK].sub.n                                 1h        +     2q                                                                                         ##STR242##                                                                          [H].sub.n                                  ______________________________________                                    

                  TABLE 16b                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR243##                                                                    ##STR244##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR245##                                                                           Polymer I(1)                              ______________________________________                                        1a        +     2c                                                                                         ##STR246##                                                                          [AI].sub.n                                 1a        +     2d                                                                                         ##STR247##                                                                          [AI].sub.n                                 1a        +     2g                                                                                         ##STR248##                                                                          [AJ].sub.n                                 1a        +     2h                                                                                         ##STR249##                                                                          [AJ].sub.n                                 1a        +     2r                                                                                         ##STR250##                                                                          [AI].sub.n                                 1a        +     2z                                                                                         ##STR251##                                                                          [A].sub.n                                  1b        +     2b                                                                                         ##STR252##                                                                          [BI].sub.n                                 1b        +     2c                                                                                         ##STR253##                                                                          [BI].sub.n                                 1b        +     2d                                                                                         ##STR254##                                                                          [BI].sub.n                                 1b        +     2f                                                                                         ##STR255##                                                                          [BJ].sub.n                                 1b        +     2g                                                                                         ##STR256##                                                                          [BJ].sub.n                                 1b        +     2h                                                                                         ##STR257##                                                                          [BJ].sub.n                                 1b        +     2r                                                                                         ##STR258##                                                                          [AIBI].sub.n                               1b        +     2s                                                                                         ##STR259##                                                                          [BI].sub.n                                 1b        +     2z                                                                                         ##STR260##                                                                          [B].sub.n                                  1c        +     2b                                                                                         ##STR261##                                                                          [CI].sub.n                                 1c        +     2c                                                                                         ##STR262##                                                                          [CI].sub.n                                 1c        +     2d                                                                                         ##STR263##                                                                          [CI].sub.n                                 1c        +     2f                                                                                         ##STR264##                                                                          [CJ].sub.n                                 1c        +     2g                                                                                         ##STR265##                                                                          [CJ].sub.n                                 1c        +     2h                                                                                         ##STR266##                                                                          [CJ].sub.n                                 1c        +     2r                                                                                         ##STR267##                                                                          [AICI].sub.n                               1c        +     2s                                                                                         ##STR268##                                                                          [BICI].sub.n                               1c        +     2t                                                                                         ##STR269##                                                                          [CI].sub.n                                 1d        +     2b                                                                                         ##STR270##                                                                          [DI].sub.n                                 1d        +     2c                                                                                         ##STR271##                                                                          [DI].sub.n                                 1d        +     2d                                                                                         ##STR272##                                                                          [DI] .sub.n                                1d        +     2f                                                                                         ##STR273##                                                                          [DJ].sub.n                                 1d        +     2g                                                                                         ##STR274##                                                                          [DJ].sub.n                                 1d        +     2h                                                                                         ##STR275##                                                                          [DJ].sub.n                                 1d        +     2j                                                                                         ##STR276##                                                                          [AD].sub.n                                 1d        +     2k                                                                                         ##STR277##                                                                          [BD].sub.n                                 1d        +     2l                                                                                         ##STR278##                                                                          [CD].sub.n                                 1d        +     2r                                                                                         ##STR279##                                                                          [AIDI].sub.n                               1d        +     2s                                                                                         ##STR280##                                                                          [BIDI].sub.n                               1d        +     2t                                                                                         ##STR281##                                                                          [CIDI].sub.n                               1d        +     2u                                                                                         ##STR282##                                                                          [DI].sub.n                                 1e        +     2b                                                                                         ##STR283##                                                                          [EI].sub.n                                 1e        +     2c                                                                                         ##STR284##                                                                          [EI].sub.n                                 1e        +     2d                                                                                         ##STR285##                                                                          [EI].sub.n                                 1e        +     2f                                                                                         ##STR286##                                                                          [EJ].sub.n                                 1e        +     2g                                                                                         ##STR287##                                                                          [EJ].sub.n                                 1e        +     2h                                                                                         ##STR288##                                                                          [EJ].sub.n                                 1e        +     2j                                                                                         ##STR289##                                                                          [AE].sub.n                                 1e        +     2k                                                                                         ##STR290##                                                                          [BE].sub.n                                 1e        +     2l                                                                                         ##STR291##                                                                          [CE].sub.n                                 1e        +     2m                                                                                         ##STR292##                                                                          [DE].sub.n                                 1e        +     2r                                                                                         ##STR293##                                                                          [AIEI].sub.n                               1e        +     2s                                                                                         ##STR294##                                                                          [BIEI].sub.n                               1e        +     2t                                                                                         ##STR295##                                                                          [CIEI].sub.n                               1e        +     2u                                                                                         ##STR296##                                                                          [DIEI].sub.n                               1e        +     2v                                                                                         ##STR297##                                                                          [EI].sub.n                                 1f        +     2b                                                                                         ##STR298##                                                                          [FI].sub.n                                 1f        +     2c                                                                                         ##STR299##                                                                          [FI].sub.n                                 1f        +     2d                                                                                         ##STR300##                                                                          [FI].sub.n                                 1f        +     2f                                                                                         ##STR301##                                                                          [FJ].sub.n                                 1f        +     2g                                                                                         ##STR302##                                                                          [FJ].sub.n                                 1f        +     2h                                                                                         ##STR303##                                                                          [FJ].sub.n                                 1f        +     2j                                                                                         ##STR304##                                                                          [AF].sub.n                                 1f        +     2k                                                                                         ##STR305##                                                                          [BF].sub.n                                 1f        +     2l                                                                                         ##STR306##                                                                          [CF].sub.n                                 1f        +     2m                                                                                         ##STR307##                                                                          [DF].sub.n                                 1f        +     2n                                                                                         ##STR308##                                                                          [EF].sub.n                                 1f        +     2r                                                                                         ##STR309##                                                                          [AIFI].sub.n                               1f        +     2s                                                                                         ##STR310##                                                                          [BIFI].sub.n                               1f        +     2t                                                                                         ##STR311##                                                                          [CIFI].sub.n                               1f        +     2u                                                                                         ##STR312##                                                                          [DIFI].sub.n                               1f        +     2v                                                                                         ##STR313##                                                                          [EIFI].sub.n                               1f        +     2w                                                                                         ##STR314##                                                                          [FI].sub.n                                 1g        +     2b                                                                                         ##STR315##                                                                          [GI].sub.n                                 1g        +     2c                                                                                         ##STR316##                                                                          [GI].sub.n                                 1g        +     2d                                                                                         ##STR317##                                                                          [GI].sub.n                                 1g        +     2f                                                                                         ##STR318##                                                                          [GJ].sub.n                                 1g        +     2g                                                                                         ##STR319##                                                                          [GJ].sub. n                                1g        +     2h                                                                                         ##STR320##                                                                          [GJ].sub.n                                 1g        +     2j                                                                                         ##STR321##                                                                          [AG].sub.n                                 1g        +     2k                                                                                         ##STR322##                                                                          [BG].sub.n                                 1g        +     2l                                                                                         ##STR323##                                                                          [CG].sub.n                                 1g        +     2m                                                                                         ##STR324##                                                                          [DG].sub.n                                 1g        +     2n                                                                                         ##STR325##                                                                          [EG].sub.n                                 1g        +     2o                                                                                         ##STR326##                                                                          [FG].sub.n                                 1g        +     2r                                                                                         ##STR327##                                                                          [AIGI].sub.n                               1g        +     2s                                                                                         ##STR328##                                                                          [BIGI].sub.n                               1g        +     2t                                                                                         ##STR329##                                                                          [CIGI].sub.n                               1g        +     2u                                                                                         ##STR330##                                                                          [DIGI].sub.n                               1g        +     2v                                                                                         ##STR331##                                                                          [EIGI].sub.n                               1g        +     2w                                                                                         ##STR332##                                                                          [FIGI[.sub.n                               1g        +     2x                                                                                         ##STR333##                                                                          [GI].sub.n                                 1h        +     2b                                                                                         ##STR334##                                                                          [HI].sub.n                                 1h        +     2c                                                                                         ##STR335##                                                                          [HI].sub.n                                 1h        +     2d                                                                                         ##STR336##                                                                          [HI].sub.n                                 1h        +     2f                                                                                         ##STR337##                                                                          [HJ].sub.n                                 1h        +     2g                                                                                         ##STR338##                                                                          [HJ].sub.n                                 1h        +     2h                                                                                         ##STR339##                                                                          [HJ].sub.n                                 1h        +     2j                                                                                         ##STR340##                                                                          [AH].sub.n                                 1h        +     2k                                                                                         ##STR341##                                                                          [BH].sub.n                                 1h        +     2l                                                                                         ##STR342##                                                                          [CH].sub.n                                 1h        +     2m                                                                                         ##STR343##                                                                          [DH].sub.n                                 1h        +     2n                                                                                         ##STR344##                                                                          [EH].sub.n                                 1h        +     2o                                                                                         ##STR345##                                                                          [FH].sub.n                                 1h        +     2p                                                                                         ##STR346##                                                                          [GH].sub.n                                 1h        +     2r                                                                                         ##STR347##                                                                          [AIHI].sub.n                               1h        +     2s                                                                                         ##STR348##                                                                          [BIHI].sub.n                               1h        +     2t                                                                                         ##STR349##                                                                          [CIHI].sub.n                               1h        +     2u                                                                                         ##STR350##                                                                          [DIHI].sub.n                               1h        +     2v                                                                                         ##STR351##                                                                          [EIHI].sub.n                               1h        +     2w                                                                                         ##STR352##                                                                          [FIHI].sub.n                               1h        +     2x                                                                                         ##STR353##                                                                          [GIHI].sub.n                               1h        +     2y                                                                                         ##STR354##                                                                          [HI].sub.n                                 ______________________________________                                    

                  TABLE 17a                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR355##                                                                    ##STR356##                                                                    Monomer (1,2)                                                                           +     Monomer (2,1)                                                                             ##STR357##                                                                           Polymer I(2)                              ______________________________________                                        1i        +     2b                                                                                         ##STR358##                                                                          [LI].sub.n                                 1i        +     2c                                                                                         ##STR359##                                                                          [LI].sub.n                                 1i        +     2d                                                                                         ##STR360##                                                                          [LI].sub.n                                 1i        +     2e                                                                                         ##STR361##                                                                          [LJ].sub.n                                 1i        +     2f                                                                                         ##STR362##                                                                          [LJ].sub.n                                 1i        +     2g                                                                                         ##STR363##                                                                          [LJ].sub.n                                 1i        +     2h                                                                                         ##STR364##                                                                          [LJ].sub.n                                 1i        +     2i                                                                                         ##STR365##                                                                          [LK].sub.n                                 1i        +     2k                                                                                         ##STR366##                                                                          [BL].sub.n                                 1i        +     2l                                                                                         ##STR367##                                                                          [CL].sub.n                                 1i        +     2m                                                                                         ##STR368##                                                                          [DL].sub.n                                 1i        +     2n                                                                                         ##STR369##                                                                          [EL].sub.n                                 1i        +     2o                                                                                         ##STR370##                                                                          [FL].sub.n                                 1i        +     2p                                                                                         ##STR371##                                                                          [GL].sub.n                                 1i        +     2q                                                                                         ##STR372##                                                                          [HL].sub.n                                 1i        +     2r                                                                                         ##STR373##                                                                          [AILI].sub.n                               1i        +     2s                                                                                         ##STR374##                                                                          [BILI].sub.n                               1i        +     2t                                                                                         ##STR375##                                                                          [CILI].sub.n                               1i        +     2u                                                                                         ##STR376##                                                                          [DILI].sub.n                               1i        +     2v                                                                                         ##STR377##                                                                          [EILI].sub.n                               1i        +     2w                                                                                         ##STR378##                                                                          [FILI].sub.n                               1i        +     2x                                                                                         ##STR379##                                                                          [GILI].sub.n                               1i        +     2y                                                                                         ##STR380##                                                                          [HILI].sub.n                               1i        +     2z                                                                                         ##STR381##                                                                          [L].sub.n                                  1j        +     2b                                                                                         ##STR382##                                                                          [MI].sub.n                                 1j        +     2c                                                                                         ##STR383##                                                                          [MI].sub.n                                 1j        +     2d                                                                                         ##STR384##                                                                          [MI] .sub.n                                1j        +     2e                                                                                         ##STR385##                                                                          [MJ].sub.n                                 1j        +     2f                                                                                         ##STR386##                                                                          [MJ].sub.n                                 1j        +     2g                                                                                         ##STR387##                                                                          [MJ].sub.n                                 1j        +     2h                                                                                         ##STR388##                                                                          [MJ].sub.n                                 1j        +     2i                                                                                         ##STR389##                                                                          [MK].sub.n                                 1j        +     2k                                                                                         ##STR390##                                                                          [BM].sub.n                                 1j        +     2l                                                                                         ##STR391##                                                                          [CM].sub.n                                 1j        +     2m                                                                                         ##STR392##                                                                          [DM].sub.n                                 1j        +     2n                                                                                         ##STR393##                                                                          [EM].sub.n                                 1j        +     2o                                                                                         ##STR394##                                                                          [FM].sub.n                                 1j        +     2p                                                                                         ##STR395##                                                                          [GM].sub.n                                 1j        +     2q                                                                                         ##STR396##                                                                          [HM].sub.n                                 1j        +     2r                                                                                         ##STR397##                                                                          [AIMI].sub.n                               1j        +     2s                                                                                         ##STR398##                                                                          [BIMI].sub.n                               1j        +     2t                                                                                         ##STR399##                                                                          [CIMI].sub.n                               1j        +     2u                                                                                         ##STR400##                                                                          [DIMI].sub.n                               1j        +     2v                                                                                         ##STR401##                                                                          [EIMI].sub.n                               1j        +     2w                                                                                         ##STR402##                                                                          [FIMI].sub.n                               1j        +     2x                                                                                         ##STR403##                                                                          [GIMI].sub.n                               1j        +     2y                                                                                         ##STR404##                                                                          [HIMI].sub.n                               1j        +     2z                                                                                         ##STR405##                                                                          [M].sub.n                                  1k        +     2b                                                                                         ##STR406##                                                                          [NI].sub.n                                 1k        +     2c                                                                                         ##STR407##                                                                          [NI].sub.n                                 1k        +     2d                                                                                         ##STR408##                                                                          [NI].sub.n                                 1k        +     2e                                                                                         ##STR409##                                                                          [NJ].sub.n                                 1k        +     2f                                                                                         ##STR410##                                                                          [NJ].sub.n                                 1k        +     2g                                                                                         ##STR411##                                                                          [NJ].sub.n                                 1k        +     2h                                                                                         ##STR412##                                                                          [NJ].sub.n                                 1k        +     2i                                                                                         ##STR413##                                                                          [NK].sub.n                                 1k        +     2k                                                                                         ##STR414##                                                                          [BN].sub.n                                 1k        +     2l                                                                                         ##STR415##                                                                          [CN].sub.n                                 1k        +     2m                                                                                         ##STR416##                                                                          [DN].sub.n                                 1k        +     2n                                                                                         ##STR417##                                                                          [EN].sub.n                                 1k        +     2o                                                                                         ##STR418##                                                                          [FN].sub.n                                 1k        +     2p                                                                                         ##STR419##                                                                          [GN].sub.n                                 1k        +     2q                                                                                         ##STR420##                                                                          [HN].sub.n                                 1k        +     2r                                                                                         ##STR421##                                                                          [AINI].sub.n                               1k        +     2s                                                                                         ##STR422##                                                                          [BINI].sub.n                               1k        +     2t                                                                                         ##STR423##                                                                          [CINI].sub.n                               1k        +     2u                                                                                         ##STR424##                                                                          [DINI].sub.n                               1k        +     2v                                                                                         ##STR425##                                                                          [EINI].sub.n                               1k        +     2w                                                                                         ##STR426##                                                                          [FINI].sub.n                               1k        +     2x                                                                                         ##STR427##                                                                          [GINI].sub.n                               1k        +     2y                                                                                         ##STR428##                                                                          [HINI].sub.n                               1k        +     2z                                                                                         ##STR429##                                                                          [N].sub.n                                  1l        +     2b                                                                                         ##STR430##                                                                          [OI].sub.n                                 1l        +     2c                                                                                         ##STR431##                                                                          [OI].sub. n                                1l        +     2d                                                                                         ##STR432##                                                                          [OI].sub.n                                 1l        +     2e                                                                                         ##STR433##                                                                          [OJ].sub.n                                 1l        +     2f                                                                                         ##STR434##                                                                          [OJ].sub.n                                 1l        +     2g                                                                                         ##STR435##                                                                          [OJ].sub.n                                 1l        +     2h                                                                                         ##STR436##                                                                          [OJ].sub.n                                 1l        +     2i                                                                                         ##STR437##                                                                          [OK].sub.n                                 1l        +     2j                                                                                         ##STR438##                                                                          [AO].sub.n                                 1l        +     2k                                                                                         ##STR439##                                                                          [BO].sub.n                                 1l        +     2l                                                                                         ##STR440##                                                                          [CO].sub.n                                 1l        +     2m                                                                                         ##STR441##                                                                          [DO].sub.n                                 1l        +     2n                                                                                         ##STR442##                                                                          [EO].sub.n                                 1l        +     2o                                                                                         ##STR443##                                                                          [FO].sub.n                                 1l        +     2p                                                                                         ##STR444##                                                                          [GO].sub.n                                 1l        +     2q                                                                                         ##STR445##                                                                          [HO].sub.n                                 1l        +     2r                                                                                         ##STR446##                                                                          [AIOI].sub.n                               1l        +     2s                                                                                         ##STR447##                                                                          [BIOI].sub.n                               1l        +     2t                                                                                         ##STR448##                                                                          [CIOI].sub.n                               1l        +     2u                                                                                         ##STR449##                                                                          [DIOI].sub.n                               1l        +     2v                                                                                         ##STR450##                                                                          [EIOI].sub.n                               1l        +     2w                                                                                         ##STR451##                                                                          [FIOI].sub.n                               1l        +     2x                                                                                         ##STR452##                                                                          [GIOI].sub.n                               1l        +     2y                                                                                         ##STR453##                                                                          [HIOI].sub.n                               1m        +     2a                                                                                         ##STR454##                                                                          [PI].sub.n                                 1m        +     2b                                                                                         ##STR455##                                                                          [PI].sub.n                                 1m        +     2c                                                                                         ##STR456##                                                                          [PI].sub.n                                 1m        +     2d                                                                                         ##STR457##                                                                          [PI].sub.n                                 1m        +     2e                                                                                         ##STR458##                                                                          [PJ].sub.n                                 1m        +     2f                                                                                         ##STR459##                                                                          [PJ].sub.n                                 1m        +     2g                                                                                         ##STR460##                                                                          [PJ].sub.n                                 1m        +     2h                                                                                         ##STR461##                                                                          [PJ].sub.n                                 1m        +     2i                                                                                         ##STR462##                                                                          [PK].sub.n                                 1m        +     2j                                                                                         ##STR463##                                                                          [AP].sub.n                                 1m        +     2k                                                                                         ##STR464##                                                                          [BP].sub.n                                 1m        +     2l                                                                                         ##STR465##                                                                          [CP].sub.n                                 1m        +     2m                                                                                         ##STR466##                                                                          [DP].sub.n                                 1m        +     2n                                                                                         ##STR467##                                                                          [EP].sub.n                                 1m        +     2o                                                                                         ##STR468##                                                                          [FP].sub.n                                 1m        +     2p                                                                                         ##STR469##                                                                          [GP].sub.n                                 1m        +     2q                                                                                         ##STR470##                                                                          [HP].sub.n                                 1m        +     2r                                                                                         ##STR471##                                                                          [AIPI].sub.n                               1m        +     2s                                                                                         ##STR472##                                                                          [BIPI].sub.n                               1m        +     2t                                                                                         ##STR473##                                                                          [CIPI].sub.n                               1m        +     2u                                                                                         ##STR474##                                                                          [DIPI].sub.n                               1m        +     2v                                                                                         ##STR475##                                                                          [EIPI].sub.n                               1m        +     2w                                                                                         ##STR476##                                                                          [FIPI].sub.n                               1m        +     2x                                                                                         ##STR477##                                                                          [GIPI].sub.n                               1m        +     2y                                                                                         ##STR478##                                                                          [HIPI].sub.n                               1n        +     2a                                                                                         ##STR479##                                                                          [QI].sub.n                                 1n        +     2b                                                                                         ##STR480##                                                                          [QI].sub.n                                 1n        +     2c                                                                                         ##STR481##                                                                          [QI].sub.n                                 1n        +     2d                                                                                         ##STR482##                                                                          [QI].sub.n                                 1n        +     2e                                                                                         ##STR483##                                                                          [QJ].sub.n                                 1n        +     2f                                                                                         ##STR484##                                                                          [QJ].sub.n                                 1n        +     2g                                                                                         ##STR485##                                                                          [QJ].sub.n                                 1n        +     2h                                                                                         ##STR486##                                                                          [QJ].sub.n                                 1n        +     2i                                                                                         ##STR487##                                                                          [QK].sub.n                                 1n        +     2j                                                                                         ##STR488##                                                                          [AQ].sub.n                                 1n        +     2k                                                                                         ##STR489##                                                                          [BQ].sub.n                                 1n        +     2l                                                                                         ##STR490##                                                                           [CQ].sub.n                                1n        +     2m                                                                                         ##STR491##                                                                          [DQ].sub.n                                 1n        +     2n                                                                                         ##STR492##                                                                          [EQ].sub.n                                 1n        +     2o                                                                                         ##STR493##                                                                          [FQ].sub.n                                 1n        +     2p                                                                                         ##STR494##                                                                          [GQ].sub.n                                 1n        +     2q                                                                                         ##STR495##                                                                          [HQ].sub.n                                 1n        +     2r                                                                                         ##STR496##                                                                          [AIQI].sub.n                               1n        +     2s                                                                                         ##STR497##                                                                          [BIQI].sub.n                               1n        +     2t                                                                                         ##STR498##                                                                          [CIQI].sub.n                               1n        +     2u                                                                                         ##STR499##                                                                          [DIQI].sub.n                               1n        +     2v                                                                                         ##STR500##                                                                          [EIQI].sub.n                               1n        +     2w                                                                                         ##STR501##                                                                          [FIQI].sub.n                               1n        +     2x                                                                                         ##STR502##                                                                          [GIQI].sub.n                               1n        +     2y                                                                                         ##STR503##                                                                          [HIQI].sub.n                               1n        +     2z                                                                                         ##STR504##                                                                          [Q].sub.n                                  1o        +     2a                                                                                         ##STR505##                                                                          [RI].sub.n                                 1o        +     2b                                                                                         ##STR506##                                                                          [RI].sub.n                                 1o        +     2c                                                                                         ##STR507##                                                                          [RI].sub.n                                 1o        +     2d                                                                                         ##STR508##                                                                          [RI].sub.n                                 1o        +     2e                                                                                         ##STR509##                                                                          [RJ].sub.n                                 1o        +     2f                                                                                         ##STR510##                                                                          [RJ].sub.n                                 1o        +     2g                                                                                         ##STR511##                                                                          [RJ].sub.n                                 1o        +     2h                                                                                         ##STR512##                                                                          [RJ].sub.n                                 1o        +     2i                                                                                         ##STR513##                                                                          [RK].sub.n                                 1o        +     2j                                                                                         ##STR514##                                                                          [AR].sub.n                                 1o        +     2k                                                                                         ##STR515##                                                                          [BR].sub.n                                 1o        +     2l                                                                                         ##STR516##                                                                          [CR].sub.n                                 1o        +     2m                                                                                         ##STR517##                                                                          [DR].sub.n                                 1o        +     2n                                                                                         ##STR518##                                                                          [ER].sub.n                                 1o        +     2o                                                                                         ##STR519##                                                                          [FR].sub.n                                 1o        +     2p                                                                                         ##STR520##                                                                          [GR].sub.n                                 1o        +     2q                                                                                         ##STR521##                                                                          [HR].sub.n                                 1o        +     2r                                                                                         ##STR522##                                                                          [AIRI].sub.n                               1o        +     2s                                                                                         ##STR523##                                                                          [BIRI].sub.n                               1o        +     2t                                                                                         ##STR524##                                                                          [CIRI].sub.n                               1o        +     2u                                                                                         ##STR525##                                                                          [DIRI].sub.n                               1o        +     2v                                                                                         ##STR526##                                                                          [EIRI].sub.n                               1o        +     2w                                                                                         ##STR527##                                                                          [FIRI].sub.n                               1o        +     2x                                                                                         ##STR528##                                                                          [GIRI].sub.n                               1o        +     2y                                                                                         ##STR529##                                                                          [HIRI].sub.n                               1o        +     2z                                                                                         ##STR530##                                                                          [R].sub.n                                  1p        +     2a                                                                                         ##STR531##                                                                          [SI].sub.n                                 1p        +     2b                                                                                         ##STR532##                                                                          [SI].sub.n                                 1p        +     2c                                                                                         ##STR533##                                                                          [SI].sub.n                                 1p        +     2d                                                                                         ##STR534##                                                                          [SI].sub.n                                 1p        +     2e                                                                                         ##STR535##                                                                          [SJ].sub.n                                 1p        +     2f                                                                                         ##STR536##                                                                          [SJ].sub.n                                 1p        +     2g                                                                                         ##STR537##                                                                          [SJ] .sub.n                                1p        +     2h                                                                                         ##STR538##                                                                          [SJ].sub.n                                 1p        +     2i                                                                                         ##STR539##                                                                          [SK].sub.n                                 1p        +     2j                                                                                         ##STR540##                                                                          [AS].sub.n                                 1p        +     2k                                                                                         ##STR541##                                                                          [BS].sub.n                                 1p        +     2l                                                                                         ##STR542##                                                                          [CS].sub.n                                 1p        +     2m                                                                                         ##STR543##                                                                          [DS].sub.n                                 1p        +     2n                                                                                         ##STR544##                                                                          [ES].sub.n                                 1p        +     2o                                                                                         ##STR545##                                                                          [FS].sub.n                                 1p        +     2p                                                                                         ##STR546##                                                                          [GS].sub.n                                 1p        +     2q                                                                                         ##STR547##                                                                          [HS].sub.n                                 1p        +     2r                                                                                         ##STR548##                                                                          [AISI].sub.n                               1p        +     2s                                                                                         ##STR549##                                                                          [BISI].sub.n                               1p        +     2t                                                                                         ##STR550##                                                                          [CISI].sub.n                               1p        +     2u                                                                                         ##STR551##                                                                          [DISI].sub.n                               1p        +     2v                                                                                         ##STR552##                                                                          [EISI].sub.n                               1p        +     2w                                                                                         ##STR553##                                                                          [FISI].sub.n                               1p        +     2x                                                                                         ##STR554##                                                                          [GISI].sub.n                               1p        +     2y                                                                                         ##STR555##                                                                          [HISI].sub.n                               ______________________________________                                    

                  TABLE 17b                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR556##                                                                    ##STR557##                                                                    Monomer (1,1) + Monomer (2,2)                                                                    ##STR558##                                                                             Polymer I(2)                                     ______________________________________                                         1a + 2hh                                                                                         ##STR559##                                                                             [AVIV'] .sub.n                                    1a + 2ii                                                                                         ##STR560##                                                                             [ATIT'] .sub.n                                    1a + 2jj                                                                                         ##STR561##                                                                             [ATKT'] .sub.n                                    1b + 2hh                                                                                         ##STR562##                                                                             [BVIV'] .sub.n                                    1b + 2ii                                                                                         ##STR563##                                                                             [BTIT'] .sub.n                                    1b + 2jj                                                                                         ##STR564##                                                                             [BTKT'] .sub.n                                    1c + 2hh                                                                                         ##STR565##                                                                             [CVIV'] .sub.n                                    1c + 2ii                                                                                         ##STR566##                                                                             [CTIT'] .sub.n                                    1c + 2jj                                                                                         ##STR567##                                                                             [CTKT'] .sub.n                                    1d + 2hh                                                                                         ##STR568##                                                                             [DVIV' ] .sub.n                                   1d + 2ii                                                                                         ##STR569##                                                                             [DTIT'] .sub.n                                    1d + 2jj                                                                                         ##STR570##                                                                             [DTKT'] .sub.n                                    1e + 2hh                                                                                         ##STR571##                                                                             [EVIV'] .sub.n                                    1e + 2hh                                                                                         ##STR572##                                                                             [ETIT'] .sub.n                                    1e + 2jj                                                                                         ##STR573##                                                                             [ETKT'] .sub.n                                    1f + 2hh                                                                                         ##STR574##                                                                             [FVIV'] .sub.n                                    1f + 2ii                                                                                         ##STR575##                                                                             [FTIT'] .sub.n                                    1f +  2jj                                                                                        ##STR576##                                                                             [FTKT'] .sub.n                                    1g + 2hh                                                                                         ##STR577##                                                                             [GVIV'] .sub.n                                    1g + 2ii                                                                                         ##STR578##                                                                             [GTIT'] .sub.n                                    1g + 2jj                                                                                         ##STR579##                                                                             [GTKT'] .sub.n                                    1h + 2hh                                                                                         ##STR580##                                                                             [HVIV'] .sub.n                                    1h + 2ii                                                                                         ##STR581##                                                                             [HTIT'] .sub.n                                    1h + 2jj                                                                                         ##STR582##                                                                             [HTKT'] .sub.n                                   ______________________________________                                    

                  TABLE 17c                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR583##                                                                    ##STR584##                                                                    Monomer (1,2) + Monomer (2,2)                                                                    ##STR585##                                                                             Polymer I(2)                                     ______________________________________                                         1i + 2hh                                                                                         ##STR586##                                                                             [LVIV'] .sub.n                                    1i + 2ii                                                                                         ##STR587##                                                                             [LTIT'] .sub.n                                    1i + 2jj                                                                                         ##STR588##                                                                             [LTKT'] .sub.n                                    1j + 2hh                                                                                         ##STR589##                                                                             [MVIV'] .sub.n                                    1j + 2ii                                                                                         ##STR590##                                                                             [MTIT'] .sub.n                                    1j + 2jj                                                                                         ##STR591##                                                                             [MTKT'] .sub.n                                    1k + 2hh                                                                                         ##STR592##                                                                             [NVIV'] .sub.n                                    1k + 2ii                                                                                         ##STR593##                                                                             [NTIT'] .sub.n                                    1k + 2jj                                                                                         ##STR594##                                                                             [NTKT'] .sub.n                                    1l + 2hh                                                                                         ##STR595##                                                                             [OVIV' ] .sub.n                                   1l + 2ii                                                                                         ##STR596##                                                                             [OTIT'] .sub.n                                    1l + 2jj                                                                                         ##STR597##                                                                             [OTKT'] .sub.n                                    1m + 2hh                                                                                         ##STR598##                                                                             [PVIV'] .sub.n                                    1m + 2ii                                                                                         ##STR599##                                                                             [PTIT'] .sub.n                                    1m + 2jj                                                                                         ##STR600##                                                                             [PTKT'] .sub.n                                    1n + 2hh                                                                                         ##STR601##                                                                             [QVIV'] .sub.n                                    1n + 2ii                                                                                         ##STR602##                                                                             [QTIT'] .sub.n                                    1n +  2jj                                                                                        ##STR603##                                                                             [QTKT'] .sub.n                                    1o + 2hh                                                                                         ##STR604##                                                                             [RVIV'] .sub.n                                    1o + 2ii                                                                                         ##STR605##                                                                             [RTIT'] .sub.n                                    1o + 2jj                                                                                         ##STR606##                                                                             [RTKT'] .sub.n                                    1p + 2hh                                                                                         ##STR607##                                                                             [SVIV'] .sub.n                                    1p + 2ii                                                                                         ##STR608##                                                                             [STIT'] .sub.n                                    1p + 2jj                                                                                         ##STR609##                                                                             [STKT'] .sub.n                                   ______________________________________                                    

EXAMPLE 26

A solution consisting of 63.34 g concentrated phosphoric acid and 147.59g of 115% PPA was stirred at 100° C. under reduced pressure for 3h in a300 ml 3-necked flask. To a 500 mL resin kettle was added 63.49 g(0.3087 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a)(prepared by the method of Wolfe, AFOSR Final Technical Report, Dec. 15,1980). A portion of the above-prepared PPA having a P₂ O₅ of 77.3%(207.57 g) was poured into the resin kettle containing the monomer whileunder argon flow. After the monomer had been incorporated, a secondportion of monomer (30.71 g, 0.1493 mol) was added. The mixture washeated to 55° C. and the pressure was gradually decreased over 1.5h. Anadditional 5.35 g of monomer was added to the kettle under argon flowbringing the total monomer added to 99.65 g (0.4845 mol). The mixturewas then stirred under reduced pressure at 50° C. overnight. Thetemperature was then raised to 70° C. for 8h. Phosphorus pentoxide(138.62 g) was then added in one portion to increase the effective P₂ O₅content to 86.4%. After heating at 100° C. with stirring overnight thereaction product was stir-opalescent. After placing the mixture, whichstill contained undissolved monomer, under reduced pressure for 3h, asample was removed and was placed between a microscope slide and a coverglass. The unprecipitated product depolarized plane-polarized light. Thereaction mixture was then heated under argon as follows: an additional2.5h at 100° C.; 2h at 120° C.; 16h at 130° C.; 31h at 170° C.; 43.5h at200° C. A sample of the green, opalescent polymer reaction productyielded gold-orange fibers upon precipitation in water. The sample wasextracted in water for 24h and dried under vacuum at 140° C. for 24h.The intrinsic viscosity was determined to be 8.2 dL/g in MSA at 30.1° C.The reaction product is characterized as having a final effective P₂ O₅content of 82.2% with the polymer --I]_(n) having a concentration of15.1% by weight.

EXAMPLE 27

A mixture of 125.8 g of 115% PPA and 53.9 g of concentrated phosphoricacid (85.7% H₃ PO₄) was heated to 100° C. for 4h under reduced pressurein a 500 mL 3-necked flask. The % P₂ O₅ content profile for this Exampleis illustrated in Example 12. To a 500 mL resin kettle was added 91.85 g(0.4466 mol) of 3a. The kettle containing the monomer was deaerated.108.17 g of the PPA prepared above (having a P₂ O₅ content of 77.2%) wasthen added. The kettle was then heated with an oil bath at 50° C. undera thin stream of argon overnight. The kettle was then placed underreduced pressure again and heated to 70° C. for 23h. P₂ O₅ (108.32 g)was then added in three portions to increase the effective P₂ O₅ contentto 88.5%. Reduced pressure was applied to degas the P₂ O₅ and to causefoaming that aided in mixing. After 3h of stirring the temperature wasraised to 100° C. and maintained at that temperture under reducedpressure for 21h. The mixture was stir-opalescent and depolarizedplane-polarized light. The mixture was then heated as follows: 115° C.under argon for 3h; 130° C. under reduced pressure for 2h; 170° C. for0.5h; 190° C. for 17h. A sample of the green, opalescent reactionproduct was removed and gave a fibrillar, golden-colored fiber upondrawing followed by precipitation in water. After extracting with waterin a Soxhlet apparatus for 24h the sample was dried for 24h at 110° C.under reduced pressure. The intrinsic viscosity of this sample was 15.8dL/g in MSA at 30° C. An additional 7.5h of heating gave a sample withan intrinsic viscosity of 16.7 dL/g. The reaction product thus obtainedwas 20.3% by weight of polymer --T]_(n) in PPA with a final P₂ O₅content of 82.4%.

EXAMPLE 28

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 146.9123 g (0.4305753 mol) of monomer 3k is dehydrochlorinated in an"initial" solution of 265.9 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 78.6 g of 85.4% H₃ PO₄ with 187.4 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 144.85g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to the schedule given in Example 27.The amount of P₂ O₅ added is preselected (as determined in accord withthe aforementioned formulae a* and b*) to provide the reaction mixturewith an effective P₂ O₅ content of approximately 85.3% prior to thestart of polymerization and an effective P₂ O₅ content of approximately82.2% subsequent to substantial complete polymerization. The reactionproduct obtained exhibits stir-opalescence and is further characterizedas having a polymer concentration of 19%; fibers are readily formed bydirect spinning, or drawing from the reaction product. The polymerobtained is of the following structure:

    --CI].sub.n

characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.which corresponds to an average n value of polymerization of about 70.

EXAMPLE 29

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3c is dehydrochlorinated in an"initial" solution of 198.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 58.7 g of 85.4% H₃ PO₄ with 140.0 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 196.8g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.6% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --U].sub.n

characterized by an intrinsic viscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 30

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3d is dehydrochlorinated in an"initial" solution of 221.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 65.50 g of 85.4% H₃ PO₄ with 156.2 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 203.1g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.2% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 18%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: characterized by an intrinsic viscosity of12 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 26-30, other Type II extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 19. The e→denotes especially preferred selected monomer reactions.

                  TABLE 19                                                        ______________________________________                                        Polymers of Type II, Class 2                                                  Polymerization Reactions:                                                      ##STR610##                                                                    Monomer (3,2)                                                                                ##STR611##                                                                             Polymer II(2)                                        ______________________________________                                         3f                                                                                           ##STR612##                                                                             [X] .sub.n                                            3g                                                                                           ##STR613##                                                                             [Y] .sub.n                                            3h                                                                                           ##STR614##                                                                             [TI] .sub.n                                           3i                                                                                           ##STR615##                                                                             [UI] .sub.n                                          ______________________________________                                    

EXAMPLE 31

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 99.923 g (0.35182 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 602.0 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 177.9 g of 85.4% H₃ PO₄ with 424.1 g of 115% PPA).When dehydrochlorination is substantially complete, 76.740 g (0.35182mol) of monomer 4a is added followed by the gradual addition of 272.7 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 84.4%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 10%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure:

    --ZB'A'B'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 31, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 20. The e→denotes especially preferred selected monomer reactions.

                  TABLE 20                                                        ______________________________________                                        Polymers of Type III, Class 1                                                 Polymerization Reactions:                                                      ##STR616##                                                                    ##STR617##                                                                    Monomer (1,1) + Monomer (4,1)                                                                    ##STR618##                                                                             Polymer III(1)                                   ______________________________________                                         1c + 4b                                                                                          ##STR619##                                                                             [B'A'F'Z] .sub.n                                   1e + 4a                                                                                         ##STR620##                                                                             [C'A'B'Z] .sub.n                                  1e + 4b                                                                                          ##STR621##                                                                             [C'A'F'Z] .sub.n                                 ______________________________________                                    

EXAMPLE 32

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 109.94 g (0.27752 mol) of monomer 11 is dehydrochlorinated inan "initial" solution of 317.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 93.7 g of 85.4% H₃ PO₄ with 223.5 g of 115% PPA).When dehydrochlorination is substantially complete, 60.533 g (0.27752mol) of monomer 4a is added followed by the gradual addition of 219.5 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: e→ p→

    --ZD'A'B'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.Analogous to the foregoing Example 32, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reactions in Table 21. The e→denotes especially preferred selected monomer reactions.

                  TABLE 21                                                        ______________________________________                                        Polymers of Type III, Class 2                                                 Polymerization Reactions:                                                      ##STR622##                                                                    ##STR623##                                                                    Monomer (1,2) + Monomer (4,1)                                                                    ##STR624##                                                                             Polymer III(2)                                   ______________________________________                                         1l + 4a                                                                                          ##STR625##                                                                             [D'A'B'Z] .sub.n                                   1l + 4b                                                                                         ##STR626##                                                                             [D'A'F'Z] .sub.n                                  1p + 4a                                                                                          ##STR627##                                                                             [E'A'B'Z] .sub.n                                  1p + 4b                                                                                          ##STR628##                                                                             [E'A'F'Z] .sub.n                                 ______________________________________                                    

EXAMPLE 33

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 117.5156 g (0.5149463 mol) of monomer 5a is dissolved in an"initial" solution of 623.7 g of PPA having a P₂ O₅ content of 77.0%(prepared by mixing 192.8 g of 85.4% H₃ PO₄ with 430.9 g of 115% PPA).When dissolution is substantially complete, an additional 257.8 g of P₂O₅ is gradually added to the mixture and dissolved by stirring andheating essentially according to Example 27. The amount of P₂ O₅ addedis preselected (as determined in accord with the aforementioned formulaea* and b*) to provide the reaction mixture with an effective P₂ O₅content of approximately 83.7% prior to the start of polymerization andan effective P₂ O₅ content of approximately 82.0% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 10%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --F'A'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 34

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.784 g (0.28869 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 242.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 71.7 g of 85.4% H₃ O₄ with 171.0 g of 115% PPA).When dehydrochlorination is substantially complete, 71.070 g (0.28869mol) of monomer 6a is added followed by the gradual addition of 162.9 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.4% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'G'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 35

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 67.798 g (0.31820 mol) of monomer 1b is dehydrochlorinated inan "initial" mixture of 343.3 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 101.4 g of 85.4% H₃ PO₄ with 241.9 g of 115% PPA).When dehydrochlorination is substantially complete, 78.336 g (0.31820mol) of monomer 6a is added followed by the gradual addition of 200.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formula a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'H'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 36

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 90.945 g (0.32021 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 402.5 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 192.1 g of 85.4% H₃ PO₄ with 210.4 g of 115% PPA).When dehydrochlorination is substantially complete, 78.830 g (0.32021mol) of monomer 6a is added followed by the gradual addition of 307.8 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.9% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'I'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 34-36, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 23. The e→denotes especially preferred selected monomer reactions.

                  TABLE 23                                                        ______________________________________                                        Polymers of Type V, Class 1                                                   Polymerization Reactions:                                                      ##STR629##                                                                    ##STR630##                                                                    Monomer (1,1) + Monomer (6,1)                                                                    ##STR631##                                                                             Polymer V(1)                                     ______________________________________                                         1d + 6a                                                                                          ##STR632##                                                                             [B'H'] .sub.n*                                    1e + 6a                                                                                          ##STR633##                                                                             [C'I'] .sub.n                                     1f + 6a                                                                                          ##STR634##                                                                             [C'H'] .sub.n                                     1g + 6a                                                                                          ##STR635##                                                                             [C'G'] .sub.n                                     1h + 6a                                                                                          ##STR636##                                                                             [B'M'] .sub.n                                    ______________________________________                                         *Note: Oxygens always para on B'-                                        

EXAMPLE 37

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 58.035 g (0.23669 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 307.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 90.9 g of 85.4% H₃ PO₄ with 216.8 g of 115% PPA).When dehydrochlorination is substantially complete. 76.281 g (0.23669mol) of monomer 6b is added followed by the gradual addition of 163.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 17%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'J'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 38

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 54.581 g (0.25617 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 330.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.6 g of 85.4% H₃ PO₄ with 232.7 g of 115% PPA).When dehydrochlorination is substantially complete, 82.559 g (0.25617mol) of monomer 6b is added followed by the gradual addition of 176.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 16%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --B'K'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 39

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 73.126 g (0.25747 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 362.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 107.1 g of 85.4% H₃ PO₄ with 255.5 g of 115% PPA).When dehydrochlorination is substantially complete, 82.978 g (0.25747mol) of monomer 6b is added followed by the gradual addition of 185.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.0% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 15%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'L'].sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 37-39, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 24a. Thee→ denotes especially preferred selected monomer reactions.

                  TABLE 24a                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR637##                                                                    ##STR638##                                                                    Monomer (1,1) + Monomer (6,2)                                                                    ##STR639##                                                                             Polymer V(2)                                     ______________________________________                                         1d + 6b                                                                                          ##STR640##                                                                             [B'K'] .sub.n*                                    1e + 6b                                                                                          ##STR641##                                                                             [C'L'] .sub.n                                     1f + 6b                                                                                          ##STR642##                                                                             [C'K'] .sub.n                                     1g + 6b                                                                                          ##STR643##                                                                             [C'J'] .sub.n                                     1h + 6b                                                                                          ##STR644##                                                                             [B'N'] .sub.n                                    ______________________________________                                         *Note: Oxygens always para on B'-                                        

EXAMPLE 40

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 76.047 g (0.23369 mol) of monomer 1i is dehydrochlorinated inan "initial" solution of 369.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.1 g of 85.4% H₃ PO₄ with 260.1 g of 115% PPA).When dehydrochlorination is substantially complete, 58.269 g (0.23369mol) of monomer 6a is added followed by the gradual addition of 180.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --D'G'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 41

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1j is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 12% fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure:

    --D'H'].sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 42

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1k is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

--D'H']_(n)

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 43

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 101.996 g (0.25747 mol) of monomer 1l is dehydrochlorinatedin an "initial" solution of 493.3 g of PPA having a P₂ O₅ content of77.3% (prepared by mixing 145.7 g of 85.4% H₃ PO₄ with 347.6 g of 115%PPA). When dehydrochlorination is substantially complete, 63.385 g(0.25747 mol) of monomer 6a is added followed by the gradual addition of221.5 g of P₂ O₅. The mixture is then stirred and heated according to aschedule similar to Example 8. The amount of P₂ O₅ added is preselected(as determined accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --D'I'].sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 40-43, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 24b and24c. The e→ and p→ denote especially preferred and preferred selectedmonomer reactions respectively.

                  TABLE 24b                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR645##                                                                    ##STR646##                                                                    Monomer (1,2) + Monomer (6,1)                                                                    ##STR647##                                                                             Polymer V(2)                                     ______________________________________                                         1m + 6a                                                                                          ##STR648##                                                                             [D'M'] .sub.n                                     1n + 6a                                                                                          ##STR649##                                                                             [E'G'] .sub.n                                     1o + 6a                                                                                          ##STR650##                                                                             [E'H'] .sub.n                                     1p + 6a                                                                                          ##STR651##                                                                             [E'I'] .sub.n                                    ______________________________________                                    

                  TABLE 24c                                                       ______________________________________                                         Monomer (1,2) + Monomer (6,2)                                                                    ##STR652##                                                                             Polymer V(2)                                     ______________________________________                                         1i + 6b                                                                                          ##STR653##                                                                             [D'J'] .sub.n                                     1j + 6b                                                                                          ##STR654##                                                                             [D'K'] .sub.n*                                    1k + 6b                                                                                          ##STR655##                                                                             [D'K'] .sub.n**                                   1l + 6b                                                                                          ##STR656##                                                                             [D'L'] .sub.n                                     1m + 6b                                                                                          ##STR657##                                                                             [D'N'] .sub.n                                     1n + 6b                                                                                          ##STR658##                                                                             [E'J'] .sub.n                                     1o + 6b                                                                                          ##STR659##                                                                             [E'K'] .sub.n                                     1p + 6b                                                                                          ##STR660##                                                                             [E'L'] .sub.n                                    ______________________________________                                         *Note: Oxygen always in 3.3'-positions on                                     **Note: Oxygens always in 4,4'-positions on D'-                          

EXAMPLE 44

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 123.074 g (0.64042 mol) of monomer 9a is dissolved in an "initial"solution of 423.1 g of PPA having a P₂ O₅ content of 77.3% (prepared bymixing 125.0 g of 85.4% H₃ PO₄ with 298.1 g of 115% PPA). Whendissolution is substantially complete, an additional 223.0 g of P₂ O₅ isgradually added to the mixture and dissolved by stirring and heatingessentially according to Example 27. The amount of P₂ O₅ added ispreselected (as determined in accord with the aforementioned formulae a*and b*) to provide the reaction mixture with an effective P₂ O₅ contentof approximately 85.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'P'].sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 45

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 86.502 g (0.30457 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 468.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 141.3 g of 85.4% H₃ PO₄ with 337.0 g of 115% PPA).When dehydrochlorination is substantially complete. 79.864 g (0.30457mol) of monomer 7a is added followed by the gradual addition of 233.0 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'O'.sub.n

characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 45, other Type VII extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration. P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 26 and27. The e→ denotes especially preferred selected monomer reactions.

                  TABLE 26                                                        ______________________________________                                        Polymers of Type VII, Class 1                                                 Polymerization Reactions:                                                      ##STR661##                                                                    ##STR662##                                                                    Monomer (1,1) + Monomer (7,1)                                                                    ##STR663##                                                                             Polymer VII(1)                                   ______________________________________                                         1e + 7a                                                                                          ##STR664##                                                                             [C'O'] .sub.n                                    ______________________________________                                    

                  TABLE 27                                                        ______________________________________                                        Polymers of Type VII, Class 2                                                 Polymerization Reactions:                                                      ##STR665##                                                                    ##STR666##                                                                    Monomer (1,2) + Monomer (7,1)                                                                    ##STR667##                                                                             Polymer VII(2)                                   ______________________________________                                         1l + 7a                                                                                          ##STR668##                                                                             [D'O'] .sub.n                                     1p + 7a                                                                                          ##STR669##                                                                             [E'O'] .sub. n                                   ______________________________________                                    

EXAMPLE 46

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 102.35 g (0.48036 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 329.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.3 g of 85.4% H₃ PO₄ with 231.9 g of 115% PPA).When dehydrochlorination is substantially complete, 67.296 g (0.48036mol) of monomer 8a is added followed by the gradual addition of 250.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 87.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'S'.sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 47

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 137.73 g (0.48494 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 370.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.6 g of 85.4% H₃ PO₄ with 261.3 g of 115% PPA).When dehydrochlorination is substantially complete, 67.939 g (0.48494mol) of monomer 8a is added followed by the gradual addition of 263.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --B'Q'.sub.n

characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 46 and 47, other Type VIII extendedchain polymers may be synthesized to yield liquid-crystallinecompositions having varying proportions of polymer concentration, P₂ O₅content and polymer intrinsic viscosity in accordance with the presentinvention.

The synthesis is illustrated by the reaction systems in Table 28. The e→and p→ denote especially preferred and preferred selected monomerreactions respectively.

                  TABLE 28                                                        ______________________________________                                        Polymers of Type VIII, Class 1                                                Polymerization Reactions:                                                      ##STR670##                                                                    ##STR671##                                                                    Monomer (1,1) + Monomer (8,1)                                                                    ##STR672##                                                                             Polymer VIII(1)                                  ______________________________________                                         1a + 8a                                                                                          ##STR673##                                                                             [B'R'] .sub.n                                     1d + 8a                                                                                          ##STR674##                                                                             [B'S' ] .sub.n                                    1e + 8a                                                                                          ##STR675##                                                                             [C'Q'] .sub.n                                     1f + 8a                                                                                          ##STR676##                                                                             [C'S'] .sub.n                                     1f + 8a                                                                                          ##STR677##                                                                             [C'R'] .sub.n                                     1h + 8a                                                                                          ##STR678##                                                                             [B'U'] .sub.n                                    ______________________________________                                    

EXAMPLE 48

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 140.33 (0.35423 mol) of monomer 1l is dehydrochlorinated inan "initial" solution of 313.01 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 92.5 g of 85.4% H₃ PO₄ with 220.5 g of 115% PPA).When dehydrochlorination is substantially complete, 49.627 g (0.35423mol) of monomer 8a is added followed by the gradual addition of 263.0 ofP₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure:

    --D'Q'.sub.n

characterized by an intrinsic viscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 49

A mixture of 123.38 g of 115% PPA and 52.63 g of concentratedorthophosphoric acid (85.7% H₃ PO₄) was stirred at 100° C. for 2 h underreduced pressure. After allowing the solution to cool to 50° C. under aflow of argon, a portion (168.18 g) of the PPA (77.3% P₂ O₅) was addedunder a flow of argon to a resin kettle containing 57.61082 g (0.23496mol, a₁ =0.95) of 1a that had been prepared as described in Example 8and 2.6358 g (0.012371 mol, a₂ =0.05) of 1b that had been prepared bythe method of Wolfe and Arnold, Macromolecules, Vol. 14, 909 (1981) andrecrystallized from hydrochloric acid containing 3 wt % of stannouschloride. The mixture was then stirred at 50° C. for 33h under reducedpressure and 90° C. for 4h under reduced pressure. Monomer 2a (41.0899g, 0.24733 mol=m, b₁ =1) was then added. The mixture was cooled toapproximately 40° C. and 139.18 g of P₂ O₅ was added to increase theeffective P₂ O₅ content before polymerization to 87.6%. The mixture wasthen stirred at the specified temperatures for the specified times undera flow of argon: 100° C. for 24h; 150° C. for 1h; 160° C. for 1h; 170°C. for 5.5 h ; and 200° C. for 64h. The final concentration of theresulting random copolymer was 16.8% in a PPA with an approximate P₂ O₅content of 82.5%. Fibers of the copolymer were isolated by drawing theresulting green, opalescent product and precipitating into water. Theintrinsic viscosity of the copolymer isolated after heating at 200° C.for 1.5 h was shown to be 25.4 dL/g and actually decreased to 24.4 dL/gafter completing the above heating schedule. The copolymer obtainedapparently is of the following structure: ##STR679## where the molefraction of AI units (a₁ b₁) is believed to be 0.95, the mole fractionof BI units (a₂ b₁) is believed to be 0.05, the average block lengthsy₁₁ and y₂₁ are believed to be 20 and 1, respectively, and the averagetotal number of recurring units of both types (n) is believed to beapproximately 100.

EXAMPLE 50

To a deaerated mixture of 16.09147 g (0.0656275 mol, a₁ =0.75) of 1a and4.66149 g (0.0218778 mol, a₂ =0.25) of 1b was added 220 g of freshlyprepared and deaerated PPA (The PPA was prepared from 173.81 g of 86.8%orthophosphoric acid and 267.64 g of phosphorous pentoxide,equilibrated, and deaerated). The mixture was stirred under an argonflow at: room temperature overnight; 50° C. for 3.5 h; and 72° C. for2121h. The mixture was stirred under reduced pressure at 72° C.overnight to substantially complete dehydrochlorination. Terephthalicacid (2a) (14.53762 g, 0.0875059 mol) was added to the solution and themixture was deaerated before stirring was initiated. The PPA preparedabove was then added to this mixture to give a total of 394.5 g of PPA.The slurry was then stirred under reduced pressure for 0.5 h at 110° C.and under an argon atmosphere at: 120° C. for 1h; 130° C. for 0.5 h;140° C. for 0.5 h; 150° C. for 0.5 h; 160° C. for 1.0 h; 170° C. for15.5 h; 185° C. for 6.5 h; and 200° C. for 19h. The opticallyanisotropic product contained 5.3 wt % polymer in PPA (84.0% P₂ O₅content). Precipitation of a small amount of the polymeric productprovided the random copolymer, believed to have the structure:##STR680## where a₁ b₁ =0.75, y₁₁ =4, a₂ b₁ =0.25, and y₂₁ =1.33, withan intrinsic viscosity of 26.59 dL/g in MSA at 30° C., which correspondsto an n value of approximately 110.

EXAMPLE 51

To a deaerated mixture of 22.36319 g (0.0912061 mol, a₁ =0.9) of 1a and2.15918 g (0.0101340 mol, a₂ =0.10) of 1b was added approximately 230 gof freshly prepared deaerated PPA. (The PPA was prepared by stirring amixture of 135.97 g of 85.4% orthophosphoric acid and 207.36 g ofphosphorous pentoxide at 150° C. overnight under an argon atmosphere,followed by deaeration by stirring under reduced pressure at 150° C. for5.5 h. The solution was allowed to cool to room temperature under agronbefore use). The mixture was stirred under an argon flow at: roomtemperature overnight; 50° C. for 3h; and at 70° C. overnight. Thesolution was then stirred under reduced pressure for 2.5 h at 70° C.Terephthalic acid (2a) (16.83595 g, 0.101340 mol); was added to thesolution and, after placing the kettle under reduced pressure, stirringwas initiated. The remaining above-mentioned PPA was then added to themixture (total PPA added=317.6 g) under an argon atmosphere. Thepolymerization mixture was then stirred under an argon atmosphere at110° C. for 30 min; 120° C. for 30 min; 130° C. for 30 min; 140° C. for30 min; 150° C. for 30 min; 160° C. for 30 min; and 170° C. for 14.5h.The polymerization mixture was heated under an argon atmosphere withoutstirring at 185° C. for 5h and at 193°-200° C. for 28h. The finalpolymer concentration was 7.6 wt % in PPA (83.0% P₂ O₅). Precipitationof a small amount of the anisotropic polymer product provided the randomcopolymer of Type IX, Class 1 with the structure: ##STR681## where a₁ b₁=0.9, a₂ b₁ =0.10, and the average block lengths y₁₁ and y₂₁ arebelieved to be 10 and 1.11, respectively. The isolated copolymerpossessed an intrinsic viscosity of 26.36 dL/g in MSA at 30° C., whichcorresponds to an n value of approximately 110.

EXAMPLE 52

A solution of 135.51 g of 115% PPA and 59.10 g of 85.7% H₃ PO₄ wasstirred at 100° C. for 2h under reduced pressure. The solution wasallowed to cool to room temperature under reduced pressure, and 180.16 gof the mixture was added to 30.20054 g of 1a under an argon atmosphere.After a homogeneous mixture was obtained 28.29941 g (58.49995 g total,0.23859 mol total=m, a₁ =1) of deaerated 1a was added. The mixture wasstirred under reduced pressure at: 50° C. for 18.5 h; 70° C. for 10 min;80° C. for 25 min; and 90° C. for 5.5 h. Deaerated 2a (35.6892 g,0.21482 mol, b₁ =0.9) and 5.79905 g (0.02394 mol, b₂ =0.10) of deaerated4,4'-biphenyldicarboxylic acid (2aa) were added under an inertatmosphere. After the monomers were incorporated into the mixture, thereaction mixture was cooled to 40° C. and 138.11 g of deaerated P₂ O₅was added to give an effective P₂ O₅ content before polymerization of87.01%. After stirring at 100° C. for 63h, the polymerization wasstirred at: 160° C. for 2.5 h; 170° C. for 5.5 h, and 200° C. for 64 h.The concentration of the resulting copolymer was 15.9% in PPA with a P₂O₅ content of approximately 82.5%. The reaction product wasstir-opalescent and was drawn into oriented fibers. The copolymerpossessed an intrinsic viscosity of 7.9 dL/g in MSA at 30° C. Thestructure of the resulting polymer is believed to be: ##STR682## wherea₁ b₁ is 0.9, a₁ b₂ is 0.1, y₁₁ is 10, y₁₂ is 1.1, and n isapproximately 40.

EXAMPLE 53

A mixture of 20.10 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 46.74 g of 115% PPA was stirred at 100° C. for 2 h under reducedpressure in a 100 mL 3-necked flask. After allowing this PPA solution,having a P₂ O₅ content of 77.3%, to cool to 50° C. under reducedpressure, a portion (82.45 g) was added under a flow of argon to a 200mL resin kettle containing 20.2783 g (0.082703 mol=m, a₁ =1) of 1a thathad been prepared and deaerated was described in Example 7. The mixturewas then stirred at the specified temperatures for the specified timesunder either reduced pressure (vac) or argon flow (Ar): 50° C. 4h, vac;50° C., 15h, Ar; 60° C., 3h, vac; 80° C., 1h, vac; 90° C., 3h, vac; 60°C., 15h, Ar; 80° C., 7h, vac. Trans-1,2-cyclohexanedicarboxylic acid (2gg) (0.6781 g, 0.004132 mol, b₂ =0.05) that as obtained from AldrichChemical Company and was recrystallized from methanol before use wasadded to the kettle and then terephthalic acid (2a) (13.05455 g,0.078579 mol, b₁ =0.95) was added. Powdered P₂ O₅ (45.00 g) was thenadded to the mixture that had been cooled to 50° C. to increase theeffective P₂ O₅ content before polymerization to 86.8%. The mixture wasthen stirred for 17h at 100° C. under an argon flow. The yellow mixturewas then heated with stirring under argon as follows: 120° C. for 1h;130°-140° C. for 1h; 150° C. for 2h; 160° C. for 0.5h; 170° C. for 4h(stir-opalescence was apparent during this time); 185° C. for 15.5h; and200° C. for 75h. The final concentration of the resulting randomcopolymer was 16.4% in PPA, with a P₂ O₅ content of approximately of82.2%. The polymer obtained apparently is of the following structure:##STR683## characterized as having an intrinsic viscosity inmethanesulfonic acid at 30° C. of 10.0 dL/g, which corresponds to anaverage n value of about 50, a mole fraction of --AI]_(n) units (a₁ b₁)of 0.95, and a mole fraction of --AA]"_(n) units (a₁ b₂) of 0.05. Theaverage block lengths, y₁₁ and y₁₂, are believed to be 20 and 1,respectively.

EXAMPLE 54

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer 1a and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR684##

EXAMPLE 55

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer )b and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR685##

EXAMPLE 56

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR686##

EXAMPLE 57

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR687##

EXAMPLE 58

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR688##

EXAMPLE 59

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR689##

EXAMPLE 60

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2 Kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR690##

EXAMPLE 61

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR691##

EXAMPLE 62

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR692##

EXAMPLE 63

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR693##

EXAMPLE 64

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1c is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR694##

EXAMPLE 65

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 2a, and 5 mol % of monomer 2gg, 100 mol % ofmonomer 1a is substantially dehydrochlorinated in a comparable weightpercent of PPA with essentially similar P₂ O₅ content. After theaddition of 75 mol % of monomer 2a and 25 mol % of monomer 2e and anappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 12 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR695##

EXAMPLE 66

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2eand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR696##

EXAMPLE 67

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 60 mol % of monomer 1a and 40 mol % of monomer 1i issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR697##

EXAMPLE 68

The procedure of Example 49 was essentially repeated. Instead of using95 mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer2a, a mixture of 80 mol % of monomer 1a and 20 mol % of monomer 1l wassubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture was then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed was anisotropic-liquid crystalline(exhibited stir-opalescence) and was formed into ordered fibers bysimple drawing. The copolymer obtained is believed to be of thefollowing structure: ##STR698##

EXAMPLE 69

The procedure of Example 69 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 85 mol % of monomer 1c and 15 mol % of monomer 1l issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR699##

EXAMPLE 70

The procedure of Example 52 is essentially repeated. Instead of using100 mol% of monomer 1a, 90 mol% of monomer 2a, and 10 mol% of monomer2aa, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2aaand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR700##

EXAMPLE 71

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2ggand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR701##

EXAMPLE 72

The procedure of Example 53 is essentially repeated. Instead of using100 mol% of monomer 1a, 95 mol% of monomer 2a, and 5 mol% of monomer2gg, 100 mol% of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol% of monomer 2a and 5 mol% of monomer 2ffand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR702##

EXAMPLE 73

Two polymerizations (Step A and Step B) were conducted simultaneously inseparate resin kettles and combined at a later stage (Step C) to give aproduct of a block copolymer believed to have the following structure:##STR703## where a₁ b₁ is 0.793 and a₁ b₂ is 0.207 and y₁₁ is greaterthan about 30.

Step A: Preparation of --AI]_(n). A mixture of 92.06g of 115% PPA and39.45g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. A portion (128.63g) of the hotPPA (77.3% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 41.42682g (0.16896 mol) of 1a. The mixture was stirred at 50°C. under argon flow for 15h, then under reduced pressure at 60° C. for23.5h, 70° C. for 6h, and 80° C. for 8.5h to effect dehydrochlorination.Terephthalic acid (2a) (28.0688g, 0.16895 mol) was then added in fourportions. The mixture was cooled to approximately 40° C. and 92.22g ofP₂ O₅ was added. The mixture was stirred at the following temperaturesfor the specified times under a flow of argon: 100° C. for 42.5h; 120°C. to 160° C. in increments of 10° C. per 0.5h; 170° C. for 2.5h. Atthis time the mixture became stir-opalescent and a sample of the dopeexhibited birefringence under plane-polarized light. After an additional3h at 170° C. the polymer from Step B was added (See Step C). Theintrinsic viscosity of Polymer --AI]_(n) isolated from the reactionmixture immediately before Step C was 2.3 dL/g which corresponds to an nvalue (average number of recurring units) of 30 and a p value (extent ofreaction) of 0.983.

Step B: Preparation of --AG"]_(n). A mixture of 30.72g of 115% PPA and13.13g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. The PPA (41.66g; 77.3% P₂ O₅)was added without cooling under a flow of argon to a resin kettlecontaining 13.80877g (0.05632 mol) of 1a. The mixture was stirred at 50°C. under argon flow for 15h, then under reduced pressure at 60° C. for23.5h, 70° C. for 6h, and 80° C. for 35.5h. Isophthalic acid (2ss)(9.3569g, 0.05632 mol) that had been obtained from Aldrich ChemicalCompany in 99% purity was twice recrystallized from 90% aqueous ethanoland dried at 110° C. for 24h and was then added in two portionsincorporating the solid after each addition. The mixture was cooled toapproximately 40° C. and then 31.59g of P₂ O₅ was added. The mixture wasthen heated simultaneously and at the same heating schedule as thesolution in Step A.

Step C: Block Copolymerization. After 5.5h at 170° C., 72g of theviscous, red, optically isotropic product from Step B was added to thekettle from Step A under an argon atmosphere at the time indicated inStep A. Both kettles were heated under an argon flow as follows: 170° C.for 12.8h; 190° C. for 2h; 200° C. for 26h. The resulting mixtureremained stir-opalescent and continued to polymerize as indicated byintrinsic viscosities of samples removed at various times. Uponprecipitation in H₂ O, the final sample of the resulting copolymer hadan intrinsic viscosity of 17.5 dL/g in MSA at 30° C. The finalprecipitated sample of the portion of the product from Step B that hadnot been added to the product from Step A (but had been heated accordingto the same schedule as the mixture) had an intrinsic viscosity of 1.8dL/g in MSA at 30° C. The weight percent of polymer --AI]_(n) in theproduct from Step A was 16.2; the weight percent of polymer --AG"]_(n)in the product from Step B was 16.3. The weight percent of blockcopolymer ##STR704## was therefore calculated to be 16.2; the weightpercents of the individual --AI]_(n) and --AG"]_(n) segments of theblock copolymer in the final product were 12.9 and 3.4, respectively, ascalculated from the weights of the constituent polymers added and thetotal weight of the resulting product. The mol percent of mesogenic--AI]_(n) and flexible --AG"]_(n) units were 79.3 and 20.7,respectively, as calculated from the weights of the constituent polymersadded.

EXAMPLE 74

Two polymerizations were conducted simultaneously in separate resinkettles (Steps A and B), and combined at a later stage (Step C) to givea block polymer product believed to have the following structure:##STR705## where a₁ b₁ is 0.587 and a₁ b₂ is 0.413 and Y₁₁ is greaterthan about 40.

Step A: Preparation of --AI]_(n). A mixture of 36.73g of 115% PPA and24.43g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (58.69%) of thehot PPA (74.9% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 20.71434g (0.08448 mol) of 1a. The mixture was stirred underreduced pressure at 50° C. for 1h, 70° C. for 1.3h, and 80° C. for 23h.To dissolve monomer, 6.02g of P₂ O₅ was added, and the kettle was heatedat 80° C. for an additional 26h. Terephthalic acid (2a) (14.0351g,0.08448 mol) was then added in three portions. The acid monomer wasincorporated by stirring after each addition. The kettle was cooled to50° C. and an additional 46.24g deaerated P₂ O₅ was added. The mixturewas stirred under argon flow at the following temperatures for thespecified times: 100° C. for 18h; 150° C. for 2h; 170° C. for 5h. (After1h at 170° C. the mixture exhibited stir-opalescence). At this time thepolymer from Step B was added. (See Step C).

Step B: Preparation of --AN"]_(n) A mixture of 63.88g of 115% PPA and42.51g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (104.41g) of thePPA (74.9% P₂ O₅) was added without cooling under a flow of argon to aresin kettle containing 20.26865g (0.08266 mol) of 1a. The mixture wasstirred under reduced pressure at 50° C. for 0.8h, 60° C. for 7.5h, and80° C. for 9.5h. Sebacic acid, (monomer 2zz, purified by crystallizationof the disodium salt, then repeated recrystallization of the free acidin H₂ O and dried in vacuo at 80° C. for 24h) (16.7190g, 0.08266 mol),was then added in three portions to the resin kettle, incorporatingafter each addition. The mixture was cooled to 50° C. and 70.91g of P₂O₅ was added slowly. The polymerization proceeded rapidly, and thegellike solid was heated without stirring at 100° C. for 16.5h and at130° C. for 7.8h. At this time the polymer was removed in an inertatmosphere, leaving a portion in the kettle which was reassembled andheated according to the same schedule as the block copolymer.

Step C: Block Copolymerization. A portion of the polymer from Step B(153.13g) was added under an argon atmosphere to the kettle from Step A.The mixture was then stirred under argon flow at 170° C. for 16h and at200° C. for 28h. The mixture remained stir-opalescent and continued topolymerize as shown by an increase in the bulk viscosity. The weightpercent of polymer --AI]_(n) in the product from Step A was 16.1; theweight percent of polymer --AN"]_(n) in the product from Step B was12.1. The weight percent of block copolymer was calculated to be 12.1;the weight percents of --AI]_(n) and --AN"]_(n) segments of the blockcopolymer in solution were 6.8 and 5.6 respectively. The mole percent ofmesogenic --AI]_(n) and --AN"]_(n) units were 58.7 and 41.3respectively, as calculated from the weights of the constituent polymersadded. The resulting polymer isolated was not completely soluble inmethane sulfonic acid thus precluding intrinsic viscosity measurements.

EXAMPLE 75

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR706##

EXAMPLE 76

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR707##

EXAMPLE 77

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR708##

EXAMPLE 78

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR709##

EXAMPLE 79

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR710##

EXAMPLE 80

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homp-oligomers) of Examples 13 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR711##

EXAMPLE 81

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 16 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR712##

EXAMPLE 82

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR713##

EXAMPLE 83

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 18 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR714##

EXAMPLE 84

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR715##

EXAMPLE 85

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 19 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR716##

EXAMPLE 86

The procedure of Example 73 essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR717##

EXAMPLE 87

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR718##

EXAMPLE 88

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2ff are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubsantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR719##

EXAMPLE 89

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2xx are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR720##

EXAMPLE 90

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2uu are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR721##

EXAMPLE 91

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1q and2a are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockplymer obtained is of the followingstructure: ##STR722##

EXAMPLE 92

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in step B, equimolar quantities of monomers 1band 2ss are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and Bdiverted into a common agitated reaction vessel in amounts to give aratio of 1.5:1. The polymerization of the resultant mixture is allowedto continue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spining or drawing and the like. The blockpolymerobtained is of the following structure: ##STR723##

EXAMPLE 93

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2xx are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR724##

EXAMPLE 94

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2zz are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR725##

EXAMPLE 95

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3c is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR726##

EXAMPLE 96

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3d is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR727##

EXAMPLE 97

The procedure of Example 27 was essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3e was substantially dehydrochlorinated in a comparable weight percentof PPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture was then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed was anisotropic-liquidcrystalline (exhibit stir-opalescence), highly drawable, and could bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is believed to be of the following struccture:##STR728##

EXAMPLE 98

The Procedure of Example 73 is essentially repeated. Subsequent to thestart of polymeriztion and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 29 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR729##

EXAMPLE 99

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR730##

EXAMPLE 100

3,4-diaminobenzoic acid (3e) (Aldrich, 97%) was recrystallized from hotwater with 3-g of carbon black and 0.5 g of sodium dithionite added forevery 30 g of 3e. The recovered light orange crystals were dried at roomtemperature under reduced pressure for 24 h. An acid mixture preparedfrom 183.4 g of 115% PPA and 78.6 g of 85.7% H₃ PO₄ (J. T. BakerAnalyzed Reagent) was deaerated by heating in a 3-necked flask at 100°C. for 2 h under reduced pressure and then at 50° C. under reducedpressure for 17 h. To a 500 mL resin kettle was added 20.24 g of 3e. Thekettle was then deaerated by applying reduced pressure and then fillingwith nitrogen three times. 51.11 g of the above-mentioned PPA was addedto the kettle and the contents stirred until well mixed. 38.77 g of P₂O₅ (J. T. Baker Analyzed Reagent, 99.1%) was added. The temperature ofthe kettle was raised to 100° C. and the P₂ O₅ incorporated into themixture. The following heating schedule was used with color changes asnoted: 100° C. for 20 min; 110° C. for 20 min; 120° C. for 20 min; 130°C. for 20 min; color changed from tan to green; 140° C. for 20 min; thegreen color became darker. Reduced pressure was briefly applied whichcaused considerable foaming; 105° C. for 20 min; 160° C. for 20 min. Asample was removed and precipitated in water to give a red polymericsubstance with an intrinsic viscosity in MSA at 30.0° C. of 4.25 dL/g.Heating at 160° C. was continued for another 30 h. The intrinsicviscosity in MSA at 30° C. of polymer component of a sample removed atthis time was measured to be 4.5 dL/g. The reaction was heated at 175°C. an additional 35 h. The resultant red-brown polymeric materialisolated from this solution had an intrinsic viscosity of 4.5 dL/g inmethanesulfonic acid at 30.0° C. Final reaction product contained 16.8%of polymer --W]_(n) in PPA. Initial P₂ O₅ content was 77.3%, final P₂ O₅content was 82.2%.

EXAMPLE 101

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR731##

EXAMPLE 102

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR732##

EXAMPLE 103

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR733##

EXAMPLE 104

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubtantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR734##

EXAMPLE 105

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completd) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR735##

EXAMPLE 106

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR736##

EXAMPLE 107

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temparature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR737##

EXAMPLE 108

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR738##

EXAMPLE 109

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR739##

EXAMPLE 110

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR740##

EXAMPLE 111

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR741##

EXAMPLE 112

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spining or drawingand the like. The blockpolymer obtained is of the following structure:##STR742##

EXAMPLE 113

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 19 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR743##

EXAMPLE 114

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 23 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR744##

EXAMPLE 115

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 22 and 27 are diverted into a commonagitated reaction of vessel in amounts to give a ratio of 1:2. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR745##

EXAMPLE 116

A mixture of 42.13 g of PPA (83.8% P₂ O₅) and 18.06 g of H₃ PO₄ (85.9%)was stirred and heated to 100° C. in a 100 ml 3-necked flask. The flaskwas placed under reduced pressure overnight. 21.34 g of3,4-diaminobenzoic acid.2HCl was added to a 100 ml resin kettle. Theresin kettle was deaerated and flushed with argon and 42.81 g of theabove prepared PPA solvent with a P₂ O₅ content of 77.32% was then addedto the kettle. The flask was heated with an oil bath at 55° C. with slowstirring under a water aspirator (reduced pressure) for 0.33 hours. Theflask was then placed under vacuum for an additional 45.87 hours. Duringthe initial 5 hours of dehydrochlorination, the temperature wasincreased from 55° C. to 70° C. Near the end of the dehydrochlorination,the mixture changed from a very pale pink to a blue-green color that wasalmost transparent. 26.56 g of deaerated P₂ O₅ was added as a powderunder argon flow. The P₂ O₅ was incorporated using a combination ofstirring and vacuum at about 70° C. The mixture was allowed toequilibrate at 100° C. with stirring under argon flow for 17.33 hours.The amount of P₂ O₅ added was calculated to provide the reaction mixturewith an effective P₂ O₅ content of approximately 86% prior to thebeginning of polymerization and an effective P₂ O₅ content ofapproximately 81.97% subsequent to substantial complete polymerization.The mixture was heated to a final temperature of 200° C. following theheating schedule outlined below.

    ______________________________________                                        Temperature                                                                             Time                                                                (°C.)                                                                            (Hours)     Observations                                            ______________________________________                                        110       0.33        Dark mint green; creamy.                                120       0.67        Less viscous.                                           130       0.38                                                                140       0.70        More viscous (mixture full                                                    of bubbles).                                            150       0.63        Darker green; shiny glass-                                                    like appearance.                                        160       0.48        Mixture riding on stir blades.                          170       0.55        Unable to stir fast; darker                                                   green.                                                  185       2.43        Mixture more transparent                                200       19.15                                                               ______________________________________                                    

The reaction product obtained is optically isotropic characterized ashaving a polymer concentration of 13.14% and an intrinsic viscosity of6.57 dL/g in MSA at 30° C. The polymer obtained is of the followingstructure:

    --W--.sub.n.

EXAMPLE 117

The reaction product of Example 13 was placed in a constant displacementspinning apparatus and extruded at about 3.4 MPa (500 psi) through a0.381 mm (0.015 in.) diameter orifice and passed through a 20.96 cm(8.25 in.) air gap at a selected take up rate to give a spin draw ratioof about 6.12:1. The extrusion temperature was about 63° C. Thecoagulation medium was water. The average tensile properties of sevensingle filaments (ASTM D 3379, 2.54 cm (1.0 in.) gage length) were 2.96GPa (4.3×10⁵ psi) tensile strength, 89.6 GPa (13×10⁶ psi) modulus, andelongation at break range from 4.2-6%. The fiber diameters ranged from33-37 micrometer (0.00129 to 0.00146 inches). Heat treated filaments(conditioned under tension at 500° C. for 60 seconds in a nitrogenatmosphere) gave average values of tensile stength 3.45 GPa (5.0×10⁵psi), modulus 317 GPa (46×10⁶ psi), and elongation at break 1.8-2.4%.The heat treated fiber diameters ranged from 29.7-33.3 micrometer(0.00117 to 0.00133 inches).

EXAMPLE 118

The procedure of Example 13 was essentially repeated using 21.0018 g(0.09857 mol) of 1b and 16.3768 g (0.09858 mol) of 2a. The P₂ O₅ contentduring dehydrochlorination was 75.16% for 8 hours and was increased to81.37% by the addition of deaerated P₂ O₅ for an additional 24 hours.The concentration of monomer 1b during dehydrochlorination was initially21.94%. After the addition of 2a, P₂ O₅ was added so as to raise the P₂O₅ content to 87.5% before polymerization and to give a P₂ O₅ contentafter substantial polymerization of 83.17%. The mixture was then heatedat 185° C. for 28 hours. The concentration of polymer --BI--_(n) was13.8 weight percent. The isolated polymer --BI--_(n) had an intrinsicviscosity of 24.4 dL/g.

EXAMPLE 119

The reaction product from Example 118 was dry-jet-wet spun as in Example117 except that the extrusion temperature was 70° C., the jet diameterwas 0.254 mm (0.010 in.), the air gap was 20.3 cm (8 in.) and therequired extrusion pressure was 1.17 MPa (170 psi). The average tensilestrength of nine single filaments was 3.12 GPa (453,000 psi) whichranged from about 2.82 to about 3.35 GPa (410,000 to 486,000 psi). Theaverage tensile modulus was 303 GPa (43.9×10⁶ psi). After treating thisfiber at 450° C. in air for 30 seconds with a 2% strength was unchangedand the modulus had increased to an average of 410 GPa (59.5×10⁶ psi).Repeating these conditions with a 2.8% stretch gave identical strengthand a modulus of 394 GPa (57.09×10⁶ psi). After treating the as spunfiber at 500° C. in air for 30 seconds with a 2.5% stretch the tensilestrength increased to an average of 3.58 GPa (519,000 psi) and themodulus increased to 467 GPa (67.8×10⁶ psi).

EXAMPLE 120

A mixture of 13.35 g of 115% PPA and 8.89 g of 85.9% H₃ PO₄ was stirredunder reduced pressure for 3.3 h at 100° C. To a 100-mL resin kettle wasadded 17.76096 g (0.09368 mol) of 3-amino-4-hydroxybenzoic acidhydrochloride (3d). The kettle was flushed with argon, and 20.45 g ofthe above PPA (P₂ O₅ content=75.2%) was added. This mixture was stirredunder reduced pressure; however, the mixture solidified overnight. 115%PPA (8.20 g, P₂ O₅ content=83.8%) was added to obtain a stirrablemixture with a P₂ O₅ content of 77.6%. After 8 h, 10.17 g of P₂ O₅ wasadded as a powder, giving a P₂ O₅ content of 83.49%. Dehydrochlorinationwas substantially complete after stirring for an additional 15 h at 80°C. Additional P₂ O.sub. 5 (12.65 g) was then added at 100° C. inaccordance with equation b* to give an f of 82.2% and an intermediate P₂O₅ content of 87.55%. The kettle was placed under reduced pressurebefore incorporating the P₂ O₅ by stirring. The mixture was then stirredfor 2.4 h at 100° C., and the temperature was increased to 140° C. After1 h at this temperature, a clear amber solution was obtained. Thetemperature was raised to 150° C. for 1 h and then raised to 185° C.After 1 h at 185° C., the reaction mixture showed a tan pearlescencewhen stirred and was birefringent when viewed at rest under crossedpolars. The reaction mixture was then heated at 185° C. for anadditional 40 h. Nearly colorless, high strength fibers were readilyformed by drawing the reaction product. The concentration of polymer--V--_(n) in the product was calculated to be 16.67%. The intrinsicviscosity of polymer --V--_(n) isolated from the product was measured tobe 13.84 dL/g in MSA at 30° C. The dried polymer had a TGA break in airat 10° C./min of 640° C. Anal. Calcd. for C₇ H₃ NO: C, 71.80; H, 2.58;N, 11.96. Found: C, 71.09; H, 2.64; N, 11.67; Residue, 0.8.

EXAMPLE 121

The reaction mixture of Example 120 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.381 mm (0.015 in.) diameter orifice into a 31.75 cm (12.5in.) air gap with a take-up rate to supply a spin draw ratio of 6.6:1.The temperature of the spinning dope was 65° C. The as spun fiber was ofpoor quanlity and very non-uniform. The as-spun properties were (340×10³psi) tensile strength, 41.3-96.5 GPa (6-14×10⁶ psi) modulus, with noelongation to break determined. After heat treatment under tension at500° C. for 60 seconds in nitrogen, the strength was essentiallyunchanged and the modulus had increased to an average value of 136 GPa(19.7×10⁶ psi).

EXAMPLE 122

The procedure of Example 120 was essentially repeated using 80.95 g(0.4269 mol) of monomer 3d, 34.37 g of 85.9% H₃ PO₄, 80.13 g of 115% PPAand 118.06 g of P₂ O₅. These amounts gave a m_(o) of 77.32%, anintermediate P₂ O₅ content of 88.83%, and (because of the loss of 1.54 gof water during polycondensation) an _(f) of 83.8%. The P₂ O₅ contentprofile for this example is graphically presented by the step-wise curveof FIG. 13. The concentration of polymer --V--_(n) in the reactionproduct was calculated to be 16.87 weight %. The total reaction timeabove 100° C. was 43.5 hours. The stir-opalescent reaction product wasbirefringent at rest and gave colorless fibers after drawing andprecipitating in water. The intrinsic viscosity of isolated polymer--V--_(n) was 12.0 dL/g.

EXAMPLE 123

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.25 mm (0.010 in.) diameter orifice into a 20.3 cm (8 in.)air gap with a take up rate to supply a spin draw ratio of 145:1. Thetemperature of the spinning dope was 90° C. The tensile strength offibers (average of nine breaks) spun from said dope was 3.57 GPa(518,000 psi). One of the fibers tested gave a break value of 5.01 GPa(727,000 psi). The average tensile modulus was 133 GPa (19.3×10⁶ psi).This value does not take into account the machine compliance. Theaverage strain at break was 3.3%. The fiber diameter was 16 micrometer(0.63×10⁻³ in.).

EXAMPLE 124

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.250 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up rate to supply a spin draw ratio of 125:1. Thetemperature of the spinning dope ws 90° C. The tensile strength offibers (average of ten breaks) spun from said dope was 2.57 GPa (373,000psi). One of the fibers tested gave a break value of 3.38 GPa (491,000psi). The average tensile modulus was 79 GPa (11.5×10⁶ psi). This valuedoes not take into account the machine compliance. The average strain atbreak was 4.6%. The fiber diameter was 19 micrometer (0.748×10⁻³ in.).

EXAMPLE 125

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.25 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up rate to supply a spin draw ratio of 100:1. Thetemperature of the spinning dope was 90° C. The tensile strength offibers (average of seven breaks) spun from said dope was 2.83 GPa(410,000 psi). One of the fibers tested gave a break value of 3.29 GPa(491,000 psi). The average tensile modulus was 61 GPa (8.8×10⁶ psi).This value does not take into account the machine compliance. Theaverage strain at break was 4.8%. The fiber diameter was 21 micrometer(0.827×10⁻³ in.).

EXAMPLE 126

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.025 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up rate to supply a spin draw ratio of 17.2:1. Thetemperature of the spinning dope was 80° C. The tensile strength offibers (average of seven breaks) spun from said dope was 2.76 GPa(400,000 psi). The average tensile modulus was 41 GPa (6.0×10⁶ psi).This value does not take into account the machine compliance. The fiberdiameter was 45 micrometer (1.76×10⁻³ in.).

EXAMPLE 127 Poly-2,5-pyridinebenzobisoxazole

A mixture of 13.25 g of concentrated orthophosphoric acid (85.9% H₃ PO₄)and 29.75 g of 115% PPA was stirred under reduced pressure at 100° C.for 2.5 hours. The resulting solution was then poured under a stream ofargon at 20° C. into a 100 ml resin kettle containing 10.8621 g(0.050980 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe, et al., Macromolecules,Vol. 14, 909 (1981), recrystallized from aqueous hydrochloric acidcontaining 3 wt % stannous chloride, and dried for 72 hours at 20° C.under reduced pressure immediately before use. The mixture was stirredat 55° C. for 18 hours, at 76° C. for 24 hours under reduced pressure.2,5-pyridinedicarboxylic acid (2i) (8.5720 g, 0.050984 mol) was thenadded under argon flow. Additional P₂ O₅ (31.18 g) was then added. Thesolution was stirred, and heated as follows: 100° C. for 1 hour; 120° C.for 3 hours; 130° C. for 0.5 hours; 140° C. for 0.5 hours; 150° C. for0.5 hours; 185° C. for 48 hours (the dark red solution becamestir-opalescent during the first hour of this last period). Theresulting product was deep red with a metallic luster, exhibitedstir-opalescence, and is further characterized as having a finaleffective P₂ O₅ content of 84% with the --BK--_(n) polymer concentrationbeing 13.4% by weight. The intrinsic viscosity of the polymer --BK--_(n)isolated from the reaction product was 4.96 dL/g in MSA at 30° C., whichcorresponds to an average number of recurring units, n, of approximately50.

EXAMPLE 128

The reaction products from Examples 27 and 120 were precipitated inwater and the polymers obtained (polymers --T--_(n) and --V--_(n),respectively) were chopped in a Waring Blender and dried. The reactionproduct from Example 12 was dry-jet wet spun into fiber (polymer--AI--_(n)) and dried. All of the precipiated polymers and spun fiber ofExamples 12, 27, and 120 including as spun fiber (polymer --BI--_(n))produced in Example 117 were tested as follows: the precipitatedpolymers and spun fibers were placed in four of the ten positions in anisothermal aging apparatus developed by SRL Laboratories of Dayton, Ohioand heated at 371° C. in circulating air for 200 hours. The apparatushas ten positions and the weight remaining in each of the positions isrecorded at 20 minute intervals. Each of the polymer samples lostapproximately 14% of their original weight initially indicating thepresence of residual volatile species (e.g. water). The weight lossesdue to isothermal aging of the individual polymers (after the initialweight loss) were as follows:

    ______________________________________                                               Polymer                                                                              Wt % Loss                                                       ______________________________________                                               --[V] .sub.n--                                                                       8.0                                                                    --[BI] .sub.n--                                                                      12.0                                                                   --[T] .sub.n--                                                                       23.0                                                                   --[AI] .sub.n--                                                                      27.0                                                            ______________________________________                                    

The results are shown graphically in FIGS. 1 and 2.

EXAMPLE 129

The samples described in Example 128 were analyzed in a Du Pont 990Thermogravimetric Analyzer at a heating rate of 5° C./min. The weightretention in He and air atmospheres (flow rate=60 ml/min) as a functionof temperature is shown for the four polymers in FIGS. 3, 4 (in He) and5, 6 (in air). The isothermal aging (see FIGS. 1 and 2) of all fourpolymers of Example 128 show a marked improvement especially forpolymers --V--_(n), --BI--_(n). Polymer --BI--_(n) can be compareddirectly with Wolfe and Loo U.S. Pat. No. 4,225,700. The improvement ispresumed to be caused by the increase in molecular weight and/or themore highly ordered morphology of the resulting polymers/fibers formedfrom compositions of the invention. Thermogravimetric analysis in air(at a heating rate of 10° C./min) was also performed on two blockpolymers of the instant invention; these block polymers were isolatedand dried from the reaction products of Example 73 and 74. The resultsof the TGA are shown in FIG. 2A.

EXAMPLE 130

A mixture of 173.59 g of concentrated orthophosphoric acid (85.5% H₃PO₄) and 414.71 g of 115% PPA was stirred under reduced pressure for 2hours. The resulting solution was then poured at approximately 30° C.under an argon stream into a 2L resin kettle containing 18.70422 g(0.557127 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe and Arnold, Macromolcules,vol. 14, 909 (1981), recrystallized from aqueous hydrochloric acidcontaining 3 wt % stannous chloride, and dried for 3.5 days at 20° C.under reduced pressure immediately before use. The mixture was stirredat 60° C. for 48 hous and 80° C. for 6 hours under reduced pressure.Monomer 2a (92.55800 g, 0.55713 mol) was then added under argon flow.Deaerated P₂ O₅ (404.45 g) was added. The mixture was then heated at100° C. for 18 hours, and 185° C. for 29 hours. The dark blue-blacksolution became stir-opalescent after 1.5 hours at 185° C. The reactionproduct was deep purple with a golden metallic luster, exhibitedstir-opalescence, and was further characterized as having a finaleffective P₂ O₅ content of 83.2%, with the --BI--_(n) polymerconcentration being 11.3% by weight. The intrinsic viscosity of thepolymer --BI--_(n) isolated from the reaction product was 20.4 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 100.

EXAMPLE 131

The reactor used for the preparation of polymer --AI--_(n) of thisExample was constructed with all wetted parts made of Hastelloy C-276.The working volume was 115 L (30 gal). Mixing was provided by fourvertical, stationary baffles attached to the reactor lid and a rotatingassembly with four vertical members. The rotating assembly was driven bya 5 hp-2.5 hp two-speed motor and had a bearing and seal at top andbottom. The reactor was charged with 13.4888 kg (55.0129 mol) of monomer1a and then with 49.1 kg of a PPA prepared from 19.64 kg of 85.8% H₃ PO₄and 29.46 kg of 115% PPA. The reactor was then heated to 60° C. within 1hour and placed under reduced pressure for 20 hours. The P₂ O₅ contentwas then raised to 78.5% by the addition of 7.751 kg of P₂ O₅ over a2-hour period, which caused the temperature to rise spontaneously to 92°C. After cooling to 68° C., an additional 5.647 kg of P₂ O₅ was added in30 minutes, causing the temperature to rise to 84° C. The mixture wasstirred at 80° C. under reduced pressure for an additional 17 hours, atwhich time all the HCl appeared to have been evolved. Monomer 2a (9.1396kg, 55.015 mol) was then added in four portions. Each portion was addedunder reduced pressure by first adding the monomer to a 12 L additionbulb, placing both the reactor and bulb under reduced pressure, and thenopening a ball valve between the two chambers. Additional P₂ O₅ (26.296kg) was then added in two portions according to equation b* to give anintermediate P₂ O₅ content of 86.26 % and a final P₂ O₅ content of82.57%. The reaction mixture was then stirred at slow speed overnight at100°-112° C. under an argon atmosphere. Using the faster stirring speed,the mixture was then heated, and samples were removed for intrinsicviscosity determinations according to the following schedule:

    ______________________________________                                        Reaction Time                                                                              Reaction Temperature                                             minutes      °C.     --[AI]--, dL/g                                    ______________________________________                                        0-12         103-112                                                          20           127                                                              27           140                                                              42           159                                                              60           172                                                              73           180                                                              87           183                                                              100          185            7.83                                              120          185            15.33                                             135          187            17.77                                             149          186            20.18                                             165          184            21.80                                             183          179                                                              ______________________________________                                    

The reaction mixture was then cooled to 110° C. over a period of fourhours, at which time the intrinsic viscosity was 24.6 dL/g. The green,opalescent product was then reheated to 130° C. and removed from thereactor for spining. A sample taken at the end of the removal wasmeasured to have an intrinsic viscosity of 27.26 dL/g. A small samplewas heated at 185° C. for an additional 24 hours, and the intrinsicviscosity rose to 34.11 dL/g.

EXAMPLE 132

A mixture of 34.97 g of PPA (83.8% P₂ O₅) and 15.00 g of H₃ PO₄ wasstirred and heated to 100° C. in a 100-ml 3-necked flask. The flask wasplaced under reduced pressure for 2.0 hours. To a 100-ml resin kettlewas added 21.32 g of 3,4-diaminobenzoic acid.2 HCl. The flask wasdeaerated and flushed with argon. 33.84 g of the above prepared PPAsolvent (having a P₂ O₅ content of 77.32%) was added to the kettle. Thekettle was heated with an oil bath at 50° C. with moderate stirringunder water-aspirator reduced pressure for 1.0 hour. The flask was thenplaced under vacuum-pump reduced pressure for an additional 46.83 hours.The temperature remained at 50° C. for 18.0 hours, at 60° C. for 1.77hours, at 70° C. for 23.81 hours, and at 80° C. for 4.25 hours. At thetime the vacuum was removed, the mixture was riding on the stir blades.Near the end of dehydrochlorination, the mixture was still opaque andthe color was mint green. The P₂ O₅ was added as a powder in twoadditions. The first addition of P₂ O₅ was in the amount of 6.93 g. TheP₂ O₅ was added under argon at 80° C. with stirring. The P₂ O₅ wasincorporated under reduced pressure. Reduced pressure was maintained for18.57 hours. The remaining 14.00 g of P₂ O₅ were added and incorporatedunder reduced pressure with stirring at 80° C. (Total P₂ O₅ =20.93 g.)The amount of P₂ O₅ added was calculated to provide the reaction mixturewith an effective P₂ O₅ content of approximately 85.99% prior to thebeginning of polymerization and an effective P₂ O₅ content ofapproximately 80.94% subsequent to substantially completepolymerization. The mixture was heated to a final temperature of 200° C.following the heating schedule outlined below.

    ______________________________________                                        Temperature                                                                              Time                                                               (°C.)                                                                             (Hours)      Observations                                          ______________________________________                                         90        0.73                                                               110        0.63         Foamy; darker green;                                                          vacuum removed.                                       120        0.72         Pea-soup green;                                                               more fluid; clearing.                                 130        0.88                                                               142        0.50                                                               152        0.17         Mixture clearer with                                                          small particles                                                               present.                                              161        0.27         Mixture full of bubbles.                              169        0.45                                                               182        0.83                                                               200        20.79                                                              ______________________________________                                    

A sample of the reaction product was stretchable, fibrous, and turnedwhite as it was drawn. The fiber was precipitated in water. The fiberand a nonprecipitated sample were birefringent at rest at roomtemperature under crossed polars. The clear green dope appeared hazy asit was cooled. The intrinsic viscosity of the reaction product was 6.58dL/g in MSA at 30° C. and the polymer concentration was 15.90%. Thepolymer obtained is of the following structure:

    --W--.sub.n.

EXAMPLE 133

A mixture of 14.71 g of concentrated orthophosphoric acid (85.9% H₃ PO₄)and 22.64 g of 115% PPA was stirred under reduced pressure at 100° C.for 2.5 hours. The resulting solution was then poured at approximately25° C. under a stream of argon into a 100 ml resin kettle containing11.04664 g (0.045053 mol) of 2,5-diamino-1,4-benzenedithioldihydrochloride (1a). The mixture was stirred under reduced pressure at50° C. for 2 hours; 60° C. for 16 hours, and 80° C. for 12.5 hours tocomplete the dehydrochlorination. Monomer 2a (7.4863 g, 0.045001 mol)was then added under an argon flow. P₂ O₅ (48.29 g) was then added. Themixture was heated at 100° C. for 3 hours and at 185° C. for 33 hours.The resulting reaction product was light green with an iridescentluster, exhibited stir-opalescence, and was further characterized ashaving a final effective P₂ O₅ content of 83.6% with the --AI--_(n)polymer concentration being 11.6 wt. %. The intrinsic viscosity of thepolymer --AI--_(n) isolated from the reaction product was 47.8 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 140.

The physical properties of as spun and heat treated fibers formed fromcompositions of Examples 117, 119, 121, 123, 124, 125, and 126 above areshown in Tables 29 and 30 below.

                                      TABLE 29                                    __________________________________________________________________________                       EXAMPLES                                                                      --[BI] .sub.n--                                                                    --[BI] .sub.n--                                                                      --[V] .sub.n--                                                                     --[V] .sub.n--                                               Example No.:                                               CONDITION          117  119    121  123                                       __________________________________________________________________________    Polymer dope                                                                   1. Intrinsic Viscosity (dL/g)                                                                   23.9 24.4   13.8 12.0                                       2. P.sub.2 O.sub.5 Content (%)                                                                  82.3 83.2   82.2 83.8                                       3. Polymer Concentration (%)                                                                    13.3 13.8   16.7 16.9                                      Spinning Conditions                                                            4. Spin Draw Ratio                                                                              6.1:1                                                                              53:1   6.6:1                                                                              145:1                                      5. Spin Temperature (°C.)                                                                63   70     65   90                                         6. Air Gap Distance (cm)                                                                        21   20.3   31.7 20.3                                       7. Jet Diameter (mm)                                                                            0.381                                                                              0.25   0.381                                                                              0.25                                       8. Dope pressure (MPa)                                                                          *2   1.17   *3.4 *3.4                                      As Spun Fiber Properties                                                       9. Tensile Strength (GPa)                                                                       2.96 3.12   2.34 3.57                                      10. Single break Tensile Strength (GPa)                                                          --   --     --   5.01                                        highest value                                                               11. Modulus (GPa)  89.6 303    41-96                                                                              133                                       12. Elongation %   4.2-6                                                                              --     --   3.3                                       13. Fiber diameter (micrometers)                                                                 33   --     37-76                                                                              16                                        Heat Treatment Conditions                                                     14. Temperature (°C.)                                                                     500  450    500  --                                        15. Time (seconds) 60   30     60   --                                        16. Stretch factor (%)                                                                           --   2      7.5  --                                        17. Atmosphere condition                                                                         Nitrogen                                                                           Air    Nitrogen                                                                           --                                        Post Heat Treatment Fiber Properties                                          18. Tensile Strength (GPa)                                                                       3.45 3.07   2.34 --                                        19. Modulus (GPa)  317  410    136  --                                        20. Elongation (%) 1.8-2.4                                                                            --     --   --                                        21. Fiber Diameter (micrometers)                                                                 31.4 --     --   --                                        22. Visual         uniform                                                                            non-uniform                                                                          --   --                                        __________________________________________________________________________     *denotes approximate values                                              

                  TABLE 30                                                        ______________________________________                                                        EXAMPLES                                                                      --[V] .sub.n--                                                                       --[V] .sub.n--                                                                         --[V] .sub.n--                                                Example No.:                                                  CONDITIONS        124      125      126                                       ______________________________________                                        Polymer dope                                                                   1. Intrinsic Viscosity (dL/g)                                                                  12.0     12.0     12.0                                       2. P.sub.2 O.sub.5 Content (%)                                                                 83.8     83.8     83.8                                       3. Polymer Concentration (%)                                                                   16.9     16.9     16.9                                      Spinning Conditions                                                            4. Spin Draw Ratio                                                                             125:1    100:1    17.2:1                                     5. Spin Temperature (°C.)                                                               90       90       80                                         6. Air Gap Distance (cm)                                                                       20.3     20.3     31.7                                       7. Jet Diameter (mm)                                                                           0.25     0.25     0.25                                       8. Dope pressure (MPa)                                                                         *3.4     *3.4     *3.4                                      As Spun Fiber Properties                                                       9. Tensile Strength (GPa)                                                                      2.57     2.83     2.76                                      10. Single break Tensile Strength                                                               3.38     3.29     --                                          (GPa)                                                                         highest value                                                               11. Modulus (GPa) 79       61       41                                        12. Elongation (%)                                                                              4.6      4.8      --                                        13. Fiber diameter (micrometers)                                                                19       21       45                                        Heat Treatment Conditions                                                     14. Temperature (°C.)                                                                    450      400      500                                       15. Time (seconds)                                                                              30       30       30                                        16. Stretch factor (%)                                                                          4.37     4.37     1.28                                      17. Atmosphere condition                                                                        Nitrogen Nitrogen Nitrogen                                  Post Heat Treatment Fiber                                                     Properties                                                                    18. Tensile Strength (GPa)                                                                      2.85     3.34     2.62                                      19. Single break tensile Strength                                                               4.94     3.76     3.00                                        (GPa)                                                                         highest value                                                               20. Modulus (GPa) 119      115      144                                       21. Elongation (%)                                                                              2.5      3.6      2.2                                       22. Fiber Diameter (micrometers)                                                                19.15    --       42.7                                      ______________________________________                                         *denotes approximate values                                              

As illustrated in the examples above, the compositions of the inventionare prepared in batch fashion, but continuous procedures may beemployed.

Some process and product benefits as a result of better control ofcertain process parameters such as shear and temperature in a continuousprocess are: (1) a more homogeneous products of reaction as a result ofa much higher order of magnitude of mixing; (2) higher throughputs; (3)and improved economics.

Another advantage of continuous processing is that the resultingreaction products can be blended in essentially all portions with otherreaction products of different polymer type and/or reaction products atdifferent stages of reaction.

In a continuous process, the aforementioned dehydrochlorination step of"Stage One" and monomer-P₂ O₅ addition of "Stage Two" are conducted at atemperature not to exceed about 100° C. in a batch reactor preferably ofthe type described in Example 131. "Stage Three" of the invention can beconducted in a motionless (static) mixer. Such mixers for paste and veryviscous materials are described in "Chemical Engineers' Handbook", R. H.Perry et al., McGraw-Hill Kogakusha, LTD., International StudentEdition, pp. 19-24, (1973); "Fluid Mixing Technology", by James Y.Oldshue, McGraw-Hill Publishing Company, pp. 431-438, (1983); and Groutet al., U.S. Pat. No.: 3,800,985. These publications and patent areincorporated herein by reference. The reaction mixture of "Stage Two" isfed from an outlet of the batch reactor through a constant displacementpump to a static mixer (tubular reactor) preferably of the typedescribed in U.S. Pat. No. 3,800,985 where the first mixing element isheated at a temperature between about 140° C. to about 185° C. Thesecond and subsequent intermediate mixing elements are heated attemperatures between about 165° C. and about 200° C. The last mixingelements are heated at temperatures between about 80° C. and about 200°C. depending on the desired temperature selected for spinning theparticular extended chain polymer employed.

In order to avoid interruptions in the continuous process, two or morebatch reactors (for conducting "Stage One" and "Stage Two") areconnected to the static mixer (tubular reactor) in parallel arrayfashion so as to feed said tubular reactor in time-wise sequence.Preferably, "Stages One and "Stage Two" can be conducted in an emptiedbatch reactor without the need for clean-up. The volume requirement ofthe tubular reactor is a function of the size and number of the batchreactor array, the desired (mixing elements) residence time, and thedesired flow rate.

Such a continuous process is especially suitable for the preparation ofblock copolymers of the present invention. Block copolymers can be madeby admixing a second reaction mixture after the first reaction mixturehas passed through an intermediate number of mixing elements.

A very important aspect of the continuous process as well as for thebatch process which must be emphasized is that "Stage One", "Stage Two",and "Stage Three" of the invention must be conducted within the shadedphosphorus pentoxide content profile area bounded by ABCDEFGHI of FIG.14. This is unrealized by the art.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above except insofar as they are defined inthe following claims.

                  APPENDIX                                                        ______________________________________                                        General Structure Reference                                                   ______________________________________                                        [A]                                                                                       ##STR746##                                                        [B]                                                                                       ##STR747##                                                        [C]                                                                                       ##STR748##                                                        [D]                                                                                       ##STR749##                                                        [E]                                                                                       ##STR750##                                                        [F]                                                                                       ##STR751##                                                        [G]                                                                                       ##STR752##                                                        [H]                                                                                       ##STR753##                                                        [I]                                                                                       ##STR754##                                                        [J]                                                                                       ##STR755##                                                        [K]                                                                                       ##STR756##                                                        [L]                                                                                       ##STR757##                                                        [M]                                                                                       ##STR758##                                                        [N]                                                                                       ##STR759##                                                        [O]                                                                                       ##STR760##                                                        [P]                                                                                       ##STR761##                                                        [Q]                                                                                       ##STR762##                                                        [R]                                                                                       ##STR763##                                                        [S]                                                                                       ##STR764##                                                        [T]                                                                                       ##STR765##                                                        [U]                                                                                       ##STR766##                                                        [V]                                                                                       ##STR767##                                                        [W]                                                                                       ##STR768##                                                        [X]                                                                                       ##STR769##                                                        [Y]                                                                                       ##STR770##                                                        [Z]                                                                                       ##STR771##                                                        [A']                                                                                      ##STR772##                                                        [B']                                                                                      ##STR773##                                                        [C']                                                                                      ##STR774##                                                        [D']                                                                                      ##STR775##                                                        [E']                                                                                      ##STR776##                                                        [F']                                                                                      ##STR777##                                                                    ##STR778##                                                        [G']                                                                                      ##STR779##                                                                    ##STR780##                                                        [H']                                                                                      ##STR781##                                                        [I']                                                                                      ##STR782##                                                                    ##STR783##                                                         [J']                                                                                     ##STR784##                                                                    ##STR785##                                                                    ##STR786##                                                         [K']                                                                                     ##STR787##                                                                    ##STR788##                                                         [L']                                                                                     ##STR789##                                                                    ##STR790##                                                        [M']                                                                                      ##STR791##                                                                    ##STR792##                                                         [N']                                                                                     ##STR793##                                                                    ##STR794##                                                        [O']                                                                                      ##STR795##                                                        [P']                                                                                      ##STR796##                                                        [Q']                                                                                      ##STR797##                                                        [R']                                                                                      ##STR798##                                                        [S']                                                                                      ##STR799##                                                        [T']                                                                                      ##STR800##                                                        [U']                                                                                      ##STR801##                                                        [V']                                                                                      ##STR802##                                                        [W']                                                                                      ##STR803##                                                        [X']                                                                                      ##STR804##                                                        [ Y']                                                                                     ##STR805##                                                        [Z']                                                                                      ##STR806##                                                        [A"]                                                                                      ##STR807##                                                        [B"]                                                                                      ##STR808##                                                        [C"]                                                                                      ##STR809##                                                        [D"]                                                                                      ##STR810##                                                        [E"]                                                                                      ##STR811##                                                        [F"]                                                                                      ##STR812##                                                        [G"]                                                                                      ##STR813##                                                        [H"]                                                                                      ##STR814##                                                        [I"]                                                                                      ##STR815##                                                        [J"]       (CH.sub.2 ) .sub.2                                                 [K"]       (CH.sub.2 ) .sub.3                                                 [L"]       (CH.sub.2 ) .sub.4                                                 [M"]       (CH.sub.2 ) .sub.5                                                 [N"]       (CH.sub.2 ) .sub.8                                                 [O"]                                                                                      ##STR816##                                                        [P"]                                                                                      ##STR817##                                                        [Q"]                                                                                      ##STR818##                                                        [R"]                                                                                      ##STR819##                                                        [S"]                                                                                      ##STR820##                                                        [T"]                                                                                      ##STR821##                                                        [U"]                                                                                      ##STR822##                                                        [V"]                                                                                      ##STR823##                                                        [W"]                                                                                      ##STR824##                                                        [X"]                                                                                      ##STR825##                                                        [Y"]                                                                                      ##STR826##                                                        [Z"]                                                                                      ##STR827##                                                        ______________________________________                                    

What we claim is:
 1. An extended chain crystalline polymer selected fromthe group consisting of: a homopolymer, a copolymer, or a block polymer,said homopolymer having the formulas: ##STR828## wherein Ar¹ is##STR829## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another and Y² is nil or is##STR830## n being a positive integer; ##STR831## wherein Ar³ is##STR832## X₃ is oxygen, or NR (R being hydrogen or an organic group),the nitrogen atom and X₃ being bonded to aromatic carbon atoms of Ar³, Nand X₃ of each hetero ring are disposed ortho to one another, n being apositive integer; ##STR833## wherein Ar¹ is ##STR834## and Ar⁴ is##STR835## the nitrogen atoms being bonded to aromatic carbon atoms ofAr¹ and the carbon atoms being bonded to aromatic carbon atoms of Ar⁴, nbeing a positive integer; ##STR836## wherein Ar⁵ is ##STR837## thenitrogen atoms being bonded to Ar⁵, n being a positive integer;##STR838## wherein Ar⁶ is ##STR839## Ar¹ is ##STR840## X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹. NH and X₁ or X₂ of each hetero ring aredisposed ortho to one another, n being a positive integer; ##STR841##wherein Ar⁹ is ##STR842## X₄ is sulfur, oxygen, or NR (R being hydrogenor an organic group), the NH group and X₄ being bonded to aromaticcarbon atoms of Ar⁹, n being a positive integer; ##STR843## wherein Ar¹is ##STR844## Y⁷ is ##STR845## the nitrogen atoms being bonded toaromatic carbon atoms of Ar¹ and bonded to adjacent carbon atoms of Y⁷,n being a positive integer; or ##STR846## wherein Ar¹ is ##STR847## Y⁸is ##STR848## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹ and adjacentcarbon atoms of Y⁸, N and X₁ and X₂ of each hetero ring are disposedortho to one another, n being a positive integer; wherein said I, II,III, IV, V, VI, VII, and VIII polymers are characterized as having amolecular weight with an n value corresponding to an intrinsic viscositygreater than about 7 dL/g as determined in methanesulfonic acid at 30°C., with the proviso that when said polymer ispoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) that themolecular weight of saidpoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity greater than 30.3 dL/g copolymerhaving the formulas: ##STR849## wherein Ar¹ is ##STR850## X₁ and X₂ arethe same or different and are sulfur, oxygen, or NR (R being hydrogen oran organic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ and X₂ of each hetero ring aredisposed ortho to one another, and Y² is nil or is ##STR851## a_(i)b_(j) represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(ij) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, n being a positive integer; ##STR852## wherein Ar¹ is##STR853## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another and Y² is nil or is##STR854## a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said copolymer, Ar³ is ##STR855## thenitrogen atom and X₃ being bonded to aromatic carbon atoms of Ar³, c_(k)m'/m+m' represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(k) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, n being a positive integer; ##STR856## wherein Ar³ is##STR857## X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₃ being bonded to aromatic carbon atomsof Ar³ , N and X₃ of each hetero ring are disposed ortho to one another,c_(k) represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(k) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, n being a positive integer; ##STR858## wherein Ar¹ is##STR859## Ar⁴ is ##STR860## the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR861## wherein Ar⁴ is ##STR862## Ar¹ is##STR863## and Ar⁵ is ##STR864## the carbon atoms being bonded to Ar⁴and Ar⁵ and the nitrogen atoms being bonded to Ar¹ and Ar⁵, n being apositive integer; c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, a_(i) b_(j) m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR865## wherein Ar¹ is##STR866## Ar⁶ is ##STR867## X₁ and X₂ are the same or different and areslfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer; ##STR868##wherein Ar⁶ is ##STR869## Ar¹ is ##STR870## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₁ and X₂ being bonded to aromatic carbonatoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hetero ring are disposedortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar⁹ is##STR871## X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₄ being bonded to aromatic carbon atoms ofAr⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;or ##STR872## wherein Ar¹ is ##STR873## Y⁷ is ##STR874## the nitrogenatoms being bonded to aromatic carbon atoms of Ar¹ and bonded toadjacent carbon atoms of Y⁷, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; wherein said copolymers X, XI, XII, XV, XVI, XVII,and XVIII are characterized as having a molecular weight with an n valuecorresponding to an intrinsic viscosity of at least about 5 dL/g asdetermined in methanesulfonic acid at 30° C. with the proviso that whensaid copolymer is IX that the molecular weight of said copolymer IXcorrespond to an intrinsic viscosity greater than 16 dL/g as determinedin methane sulfonic acid at 30° C.; said block polymer having theformulas: ##STR875## wherein Ar¹ is ##STR876## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbonatoms of Ar¹, N and X₁ and X₂ of each hetero ring are disposed ortho toone another and Y² is nil or is ##STR877## a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR878## wherein Ar³ is##STR879## X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atom and X₃ being bonded to aromatic carbon atomsof Ar³, N and X₃ of each hereto ring are disposed ortho to one another,c_(k) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(k) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer; ##STR880##wherein Ar¹ is ##STR881## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹ , N and X₁ and X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR882## a_(i) b_(j) m/m+m' represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer. Ar³ is ##STR883## X₃ is sulfur, oxygen, or NR (R being hydrogenor an organic group), the nitrogen atom and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of each hetero ring are disposed ortho toone another, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; ##STR884## wherein Ar¹ is ##STR885## Ar⁴ is ##STR886##the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR887## wherein Ar¹ is ##STR888## when bonded to nitrogenatoms; and when Ar¹ is bonded to both nitrogen atoms and X₁ and X₂, Ar¹is ##STR889## Ar⁴ is ##STR890## the nitrogen atoms being bonded to Ar¹and the carbon atoms being bonded to Ar⁴, m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y' represents an average number of the respectivedifferent sequential recurring units present in said block polymer, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another and Y² is nil or is ##STR891##m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer; ##STR892## wherein Ar³is ##STR893## X₃ is sulfur, oxygen, or NR (R being hydrogen or anorganic group). the nitrogen atoms and X₃ being bonded to aromaticcarbon atoms of Ar³. N and X₃ of each hetero ring are disposed ortho toone another, p represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y'/2 representsan average number of the respective different sequential recurring unitspresent in said block polymer, Ar¹ is ##STR894## Ar⁴ is ##STR895## thenitrogen atoms being bonded to Ar¹ and the carbon atoms being bonded atAr⁴, q represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer; ##STR896## wherein Ar⁴is ##STR897## Ar¹ is ##STR898## and Ar⁵ is ##STR899## the carbon atomsbeing bonded to Ar⁴ and Ar⁵, and the nitrogen atoms being bonded to Ar¹and Ar⁵, n being a positive integer; c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said block polymer,a_(i) b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer. y_(ij)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR900## wherein Ar¹ is ##STR901## Ar⁶ is ##STR902## X₁ andX₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹. NH and X₁ or X₂ of each heteroring are disposed ortho to one another, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR903## wherein Ar¹ is ##STR904## Ar⁶ is##STR905## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂of each hetero ring are disposed ortho to one another, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, Ar⁹ is ##STR906## X₄ is sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₄ beingbonded to aromatic carbon atoms of Ar⁶ and Ar⁹, c_(k) m /m+m' representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y_(k) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; or ##STR907## wherein Ar¹ is##STR908## Y⁷ is ##STR909## the nitrogen atoms being bonded to aromaticcarbon atoms of Ar¹ and bonded to adjacent carbon atoms of Y⁷, a_(i)b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 2. Anextended chain crystalline polymer having the general formulas:##STR910## wherein Ar¹ is ##STR911## X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atomsof Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR912## n being a positive integer;##STR913## wherein Ar³ is ##STR914## X₃ is sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the nitrogen atoms and X₃ beingbonded to aromatic carbon atoms of Ar³, N and X₃ of each hetero ring aredisposed ortho to one another, n being a positive integer; ##STR915##wherein Ar¹ is ##STR916## and Ar⁴ is ##STR917## the nitrogen atoms beingbonded to aromatic carbon atoms of Ar¹ and the carbon atoms being bondedto aromatic carbon atoms of Ar⁴, n being a positive integer; ##STR918##wherein Ar⁵ is ##STR919## the nitrogen atoms being bonded to Ar⁵, nbeing a positive integer; ##STR920## wherein Ar⁶ is ##STR921## Ar¹ is##STR922## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂of each hetero ring are disposed ortho to one another, n being apositive integer; ##STR923## wherein Ar⁹ is ##STR924## X₄ is sulfur,oxygen or NR (R being hydrogen or an organic group), the NH group and X₄being bonded to aromatic carbon atoms of Ar⁹, n being a positiveinteger; ##STR925## wherein Ar¹ is ##STR926## Y⁷ is ##STR927## thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer; or##STR928## wherein Ar¹ is ##STR929## Y⁸ is ##STR930## X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹ and adjacent carbon atoms of Y⁸, N and X₁or X₂ of each hetero ring are disposed ortho to one another, n being apositive integer, wherein said polymers I, II, III, IV, V, VI, VII, andVIII are characterized as having a molecular weight with an n valuecorresponding to an intrinsic viscosity greater than about 7 dL/g asdetermined in methanesulfonic acid at 30° C., with the proviso that whensaid polymer is poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) that the molecular weight of saidpoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity greater than 30.3 dL/g asdetermined in methanesulfonic acid at 30° C.
 3. An extended chaincrystalline polymer having the general formula: ##STR931## wherein Ar¹is ##STR932## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ orX₂ of each hetero ring are disposed ortho to one another and Y² is nilor is ##STR933## n being a positive integer; wherein said polymer ischaracterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 7 dl/g as determined inmethanesulfonic acid at 30° C., with the proviso that when said polymeris poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) thatthe molecular weight of saidpoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity greater than 30.3 dl/g asdetermined in methanesulfonic acid at 30° C.
 4. An extended chaincrystalline homopolymer having the general formula: ##STR934## whereinAr¹ is ##STR935## X₁ and X₂ are the same or different and are oxygen, orNR (R being hydrogen or an organic group), the nitrogen atoms and X₁ andX₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of eachhetero ring are disposed ortho to one another and Y² is nil or is##STR936## n being a positive integer, wherein said homopolymer ischaracterized as having a molecular weight with an n value correspondingto an intrinstic viscosity greater than about 7 dL/g as determined inmethanesulfonic acid at 30° C.
 5. A polymer of claim 1, wherein saidpolymer is an extended chain crystalline homopolymer having the generalformula: ##STR937## wherein Ar³ is ##STR938## X₃ is sulfur, oxygen, orNR (R being hydrogen or an organic group), the nitrogen atom and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, n being a positive integer,wherein said homopolymer is characterized as having a molecular weightwith an n value corresponding to an intrinsic viscosity greater thanabout 5 dL/g as determined in methanesulfonic acid at 30° C.
 6. Apolymer of claim 1, wherein said polymer is an extended chaincrystalline homopolymer having the general formula: ##STR939## whereinAr¹ is ##STR940## and Ar⁴ is ##STR941## the nitrogen atoms being bondedto aromatic carbon atoms of Ar¹ and the carbon atoms being bonded toaromatic carbon atoms of Ar⁴, n being a positive integer, wherein saidpolymer is characterized as having a molecular weight with an n valuecorresponding to an intrinsic viscosity of at least about 5 dL/g asdetermined in methanesulfonic acid at 30° C., with the proviso that whensaid polymer is poly(6,9-dihydro-6,9-dioxobisbenzimidazo [2,1-b:1',2'-j]benzo[1mn][3,8]phenanthroline-2,3, 12, 13-tetrayl) that themolecular weight of saidpoly(6,9-dihydro-6,9-dioxobisbenzimidazo-[2,1-b:1',2'-j]benzo[1mn][3,8]phenanthroline-2,3,12,13-tetrayl) corresponding toan intrinsic viscosity greater than 7 dL/g as determined inmethanesulfonic acid at 30° C.
 7. A polymer of claim 1, wherein saidpolymer is an extended chain crystalline homopolymer having the generalformula: ##STR942## wherein Ar⁵ is ##STR943## the nitrogen atoms beingbonded to Ar⁵, n being a positive integer, wherein said homopolymer ischaracterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 5 dL/g as determined inmethanesulfonic acid at 30° C.
 8. A polymer of claim 1, wherein saidpolymer is an extended chain crystalline homopolymer having the generalformula: ##STR944## wherein Ar⁶ is ##STR945## Ar¹ is ##STR946## X₁ andX₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, n being a positive integer,wherein said homopolymer is characterized as having a molecular weightwith an n value corresponding to an intrinsic viscosity greater thanabout 5 dL/g as determined in methanesulfonic acid at 30° C.
 9. Apolymer of claim 1, wherein said polymer is an extended chaincrystalline homopolymer having the general formula: ##STR947## whereinAr⁹ is ##STR948## X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH group and X₄ being bonded to aromatic carbonatoms of Ar⁹, n being a positive integer, wherein said homopolymer ischaracterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 5 dL/g as determined inmethanesulfonic acid at 30° C.
 10. A polymer of claim 1, wherein saidpolymer is an extended chain crystalline homopolymer having the generalformula: ##STR949## wherein Ar¹ is ##STR950## Y⁷ is ##STR951## thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer, wherein saidhomopolymer is characterized as having a molecular weight with an nvalue corresponding to an intrinsic viscosity greater than about 5 dL/gas determined in methanesulfonic acid at 30° C.
 11. A polymer of claim1, wherein said polymer is an extended chain crystalline homopolymerhaving the general formula: ##STR952## wherein Ar¹ is ##STR953## Y⁸ is##STR954## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹ and adjacent carbonatoms of Y⁸, N and X₁ or X₂ of each hetero ring are disposed ortho toone another, n being a positive integer, wherein said homopolymer ischaracterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 5 dL/g as determined inmethanesulfonic acid at 30° C.
 12. A polymer of claim 1, wherein saidpolymer is a formula I extended chain crystalline homopolymer having theformulas: ##STR955## wherein n is greater than
 60. 13. A polymer ofclaim 1, wherein said polymer is a formula I extended chain crystallinehomopolymer having the formula: ##STR956## wherein n is greater than 30.14. A polymer of claim 1, wherein said polymer is a formula I extendedchain crystalline homopolymer having the formula: ##STR957## wherein nis greater than
 110. 15. A polymer of claim 1, wherein said polymer is aformula I extended chain crystalline homopolymer having the formula:##STR958## wherein n is greater than
 60. 16. A polymer of claim 1,wherein said polymer is a formula I extended chain crystallinehomopolymer having the formulas: ##STR959## wherein n is greater than50.
 17. A polymer of claim 1, wherein said polymer is a formula Iextended chain crystalline homopolymer having the formula: ##STR960##wherein n is greater than
 70. 18. A polymer of claim 1, wherein saidpolymer is a formula I extended chain crystalline homopolymer having theformula: ##STR961## wherein n is greater than
 60. 19. A polymer of claim1, wherein said polymer is a formula I extended chain crystallinehomopolymer having the formulas: ##STR962## wherein n is greater than60.
 20. A polymer of claim 1, wherein said polymer is a formula IIextended chain crystalline homopolymer having the formula: ##STR963##wherein n is greater than
 60. 21. A polymer of claim 1, wherein saidpolymer is a formula II extended chain crystalline homopolymer havingthe formula: ##STR964## wherein n is greater than
 60. 22. A polymer ofclaim 1, wherein said polymer is a formula III extended chaincrystalline homopolymer having the formulas: ##STR965## wherein n isgreater than
 50. 23. A polymer of claim 1, wherein said polymer is aformula III extended chain crystalline homopolymer having the formulas:##STR966## wherein n is greater than
 60. 24. A polymer of claim 1,wherein said polymer is a formula IV extended chain crystallinehomopolymer having the formula: ##STR967## wherein n is greater than 70.25. A polymer of claim 1, wherein said polymer is a formula V extendedchain crystalline homopolymer having the formulas: ##STR968## wherein nis greater than
 30. 26. A polymer of claim 1, wherein said polymer is aformula V extended chain crystalline homopolymer having the formula:##STR969## wherein n is greater than
 30. 27. A polymer of claim 1,wherein said polymer is a formula V extended chain crystallinehomopolymer having the formula: ##STR970## wherein n is greater than 30.28. A polymer of claim 1, wherein said polymer is a formula V extendedchain crystalline homopolymer having the formulas: ##STR971## wherein nis greater than
 30. 29. A polymer of claim 1, wherein said polymer is aformula V extended chain crystalline homopolymer having the formulas:##STR972## wherein n is greater than
 30. 30. A polymer of claim 1,wherein said polymer is a formula V extended chain crystallinehomopolymer having the formulas: ##STR973## wherein n is greater than30.
 31. A polymer of claim 1, wherein said polymer is a formula Vextended chain crystalline homopolymer having the formula: ##STR974##wherein n is greater than
 30. 32. A polymer of claim 1, wherein saidpolymer is a formula V extended chain crystalline homopolymer having theformulas: ##STR975## wherein n is greater than
 30. 33. A polymer ofclaim 1, wherein said polymer is a formula VI extended chain crystallinehomopolymer having the formula: ##STR976## wherein n is greater than 30.34. A polymer of claim 1, wherein said polymer is a formula VII extendedchain crystalline homopolymer having the formula: ##STR977## wherein nis greater than
 30. 35. A polymer of claim 1, wherein said polymer is aformula VIII extended chain crystalline homopolymer having the formulas:##STR978## wherein n is greater than
 40. 36. A polymer of claim 1,wherein said polymer is a formula VIII extended chain crystallinehomopolymer having the formula: ##STR979## wherein n is greater than 30.37. A polymer of claim 1, wherein said polymer is a formula VIIIextended chain crystalline homopolymer having the formula: ##STR980##wherein n is greater than
 30. 38. A polymer of claim 1, wherein saidpolymer is a formula VIII extended chain crystalline homopolymer havingthe formulas: ##STR981## wherein n is greater than
 30. 39. A polymer ofclaim 1, wherein said polymer is a formula VIII extended chaincrystalline homopolymer having the formulas: ##STR982## wherein n isgreater than
 30. 40. A polymer of claim 1, wherein said polymer is anextended chain crystalline copolymer having the general formulas:##STR983## wherein Ar¹ is ##STR984## X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atomsof Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, and Y² is nil or is ##STR985## a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer: ##STR986## wherein Ar¹ is ##STR987## X₁ and X₂ arethe same or different and are sulfur, oxygen, or NR (R being hydrogen oran organic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y₂ is nil or is ##STR988## a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(ij) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, Ar³ represents a different aromatic moiety and is##STR989## the nitrogen atom and X₃ being bonded to aromatic carbonatoms of Ar³, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer:##STR990## wherein Ar³ is ##STR991## X₃ is sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the nitrogen atoms and X₃ beingbonded to aromatic carbon atoms of Ar³, N and X₃ of each hetero ring aredisposed ortho to one another, c_(k) represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(k) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger: ##STR992## wherein Ar¹ is ##STR993## Ar⁴ is ##STR994## thenitrogen atoms being bonded to Ar¹ and the carbon atoms being bonded toAr⁴, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer: ##STR995##wherein Ar⁴ is ##STR996## Ar¹ is ##STR997## and Ar⁵ is ##STR998## thecarbon atoms being bonded to Ar⁴ and Ar⁵ and the nitrogen atoms beingbonded to Ar¹ and Ar⁵, n being a positive integer; c_(k),'/m+m'represents the molar proportions of the respective different recurringunits present in said copolymer, y_(k) represents an average number ofthe respective different sequential recurring units present in saidcopolymer, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;##STR999## wherein Ar¹ is ##STR1000## Ar⁶ is ##STR1001## X₁ and X₂ arethe same or different and are sulfur, oxygen, or NR (R being hydrogen oran organic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hetero ring aredisposed ortho to one another, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR1002## wherein Ar⁶ is ##STR1003## Ar¹ is##STR1004## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂of each hetero ring are disposed ortho to one another, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(ij) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, Ar⁹ is ##STR1005## X₄ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₄ being bonded toaromatic carbon atoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer: or ##STR1006## wherein Ar¹ is ##STR1007## Y⁷ is##STR1008## the nitrogen atoms being bonded to aromatic carbon atoms ofAr¹ and bonded to adjacent carbon atoms of Y⁷, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer, wherein said copolymers X, XI,XII, XV, XVI, XVII, and XVIII are characterized as having a molecularweight with an n value corresponding to an intrinsic viscosity of atleast about 5 dL/g as determined in methanesulfonic acid at 30° C. withthe proviso that when said polymer is IX that the molecular weight ofsaid IX polymer correspond to an intrinsic viscosity greater than 16dL/g as determined in methanesulfonic acid at 30° C.
 41. A polymer ofclaim 1, wherein said polymer is an extended chain crystalline copolymerhaving the general formula: ##STR1009## wherein Ar¹ is ##STR1010## X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another, and Y² is nil or is ##STR1011##a_(i) b_(j) represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(ij) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, n being a positive integer, wherein said copolymer ischaracterized as having a molecular weight with an n value correspondingto an intrinsic viscosity of greater than about 16 dL/g as determined inmethanesulfonic acid at 30° C.
 42. A polymer of claim 1, wherein saidpolymer is an extended chain crystalline copolymer having the generalformula: ##STR1012## wherein Ar³ is ##STR1013## X₃ is sulfur, oxygen, orNR (R being hydrogen or an organic group), the nitrogen atoms and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, c_(k) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer, wherein said copolymer is characterized as having amolecular weight with an n value corresponding to an intrinsic viscosityof greater than about 5 dL/g as determined in methanesulfonic acid at30° C.
 43. A polymer of claim 1, wherein said polymer is an extendedchain crystalline copolymer having the general formula: ##STR1014##wherein Ar¹ is ##STR1015## X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR1016## a_(i) b_(j) m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, Ar³ is ##STR1017## the nitrogen atom and X₃ being bonded toaromatic carbon atoms of Ar³, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer, wherein said copolymer is characterized as having amolecular weight with an n value corresponding to an intrinsic viscosityof greater than about 5 dL/g as determined in methanesulfonic acid at30° C.
 44. A polymer of claim 1, wherein said polymer is an extendedchain crystalline copolymer having the general formula: ##STR1018##wherein Ar¹ is ##STR1019## Ar⁴ is ##STR1020## the nitrogen atoms beingbonded to Ar¹ and the carbon atoms being bonded to Ar⁴, a_(i) b_(j)represents the molar proportions of the respective different recurringunits present in said copolymer, y_(ij) represents an average number ofthe respective different sequential recurring units present in saidcopolymer, n being a positive integer.
 45. A polymer of claim 1, whereinsaid polymer is an extended chain crystalline copolymer having thegeneral formula: ##STR1021## wherein Ar⁴ is ##STR1022## Ar¹ is##STR1023## and Ar⁵ is ##STR1024## the carbon atoms being bonded to Ar⁴and Ar⁵ and the nitrogen atoms being bonded to Ar¹ and Ar⁵, n being apositive integer; c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, a_(i) b_(j) m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer.
 46. A polymer of claim 1, whereinsaid polymer is an extended chain crystalline copolymer having thegeneral formula: ##STR1025## wherein Ar¹ is ##STR1026## Ar⁶ is##STR1027## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂of each hetero ring are disposed ortho to one another, a_(i) b_(j)represents the molar proportions of the respective different recurringunits present in said copolymer, y_(ij) represents an average number ofthe respective different sequential recurring units present in saidcopolymer, n being a positive integer.
 47. A polymer of claim 1, whereinsaid polymer is an extended chain crystalline copolymer having thegeneral formula: ##STR1028## wherein Ar⁶ is ##STR1029## Ar¹ is##STR1030## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, Nh and X₁ or X₂of each hetero ring are disposed ortho to one another, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said copolymer, y_(ij) represents an averagenumber of the respective different sequential recurring units present insaid copolymer, Ar⁹ is ##STR1031## X₄ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₄ being bonded toaromatic carbon atoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer.
 48. A polymer of claim 1, wherein said polymer is anextended chain crystalline copolymer having the general formula:##STR1032## wherein Ar¹ is ##STR1033## Y⁷ is ##STR1034## the nitrogenatoms being bonded to aromatic carbon atoms of Ar¹ and bonded toadjacent carbon atoms of Y⁷, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer.
 49. A polymer of claim 1, wherein said polymer is aformula IX extended chain crystalline copolymer having the formulas:##STR1035## wherein a₁ b₁ and a₁ b₂ or a₂ b₁ are the said molarproportions of the respective different recurring units, a₁ b₁ beingbetween zero and about one, a₁ b₂ or a₂ b₁ being equal to 1-a₁ b₁ ;wherein y₁₁ and y₁₂ or y₂₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being at least greater thanabout one and less than about 75, y₁₂ or y₂₁ being at least greater thanone and less than about 75, n being an average number of total recurringunits greater than about 50 and less than about
 150. 50. A polymer ofclaim 1, wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1036## wherein a₁ b₁ and a₁ b₂ arethe said molar proportions of the respective different recurring units,a₁ b₁ being between about 0.9 and one, a₁ b₂ being equal to 1-a₁ b₁ ;wherein y₁₁ and y₁₂ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being at least about 10, y₁₂being about one, n being at least about 50 and less than about
 150. 51.A polymer of claim 1, wherein said polymer is a formula IX extendedchain crystalline copolymer having the formulas: ##STR1037## wherein a₁b₁ and a₁ b₂ are the said molar proportions of the respective differentrecurring units, a₁ b₁ being between about 0.95 and 1, a₁ b₂ being equalto 1-a₁ b₁ ; wherein y₁₁ and y₁₂ are the said average number of therespective different sequential recurring units, y₁₁ being at leastabout 20, y₁₂ being about one, n being at least about 50 and less thanabout
 150. 52. A polymer of claim 1, wherein said polymer is a formulaIX extended chain crystalline copolymer having the formulas: ##STR1038##wherein a₁ b₁ and a₂ b₁ are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ being between zero and about one, a₂ b₁being equal to 1-a₁ b₁ ; wherein y₁₁ and y₂₁ are the said average numberof the respective different sequential recurring units, y₁₁ being atleast about one, y₂₁ being about one, n being at least about 50 and lessthan about
 150. 53. A polymer of claim 1, wherein said polymer is aformula IX extended chain crystalline copolymer having the formulas:##STR1039## wherein a₁ b₁ and a₂ b₁ are the said molar proportions ofthe respective different recurring units, a₁ b₁ being between about 0.75and one, a₂ b₁ being equal to 1-a₁ b₁ ; wherein y₁₁ and y₂₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being at least about 4, y₂₁ being about 1.3, n being at least about50 and less than about
 150. 54. A polymer of claim 1, wherein saidpolymer is a formula IX extended chain crystalline copolymer having theformulas: ##STR1040## wherein a₁ b₁ and a₂ b₁ are the said molarproportions of the respective different recurring units, a₁ b₁ beingbetween about 0.75 and one, a₂ b₁ being equal to 1-a₁ b₁ ; wherein y₁₁and y₂₁ are the said average number of the respective differentsequential recurring units, y₁₁ being at least about 4, y₁₂ being about1.3, n being at least about 50 and less than about
 150. 55. A polymer ofclaim 1, wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1041## wherein a₁ b₁ and a₂ b₁ arethe said molar proportions of the respective different recurring units,a₁ b₁ being between about 0.8 and one, a₂ b₁ being equal to 1-a₁ b₁ ;wherein y₁₁ and y₂₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being at least about 5, y₂₁being about 1.2, n being at least about 50 and less than about
 120. 56.A polymer of claim 1, wherein said polymer is a formula IX extendedchain crystalline copolymer having the formulas: ##STR1042## wherein a₁b₁ and a₁ b₂ are the said molar proportions of the respective differentrecurring units, a₁ b₁ being between about 0.9 and one, a₁ b₂ beingequal to 1-a₁ b₁ ; wherein y₁₁ and y₁₂ are the said average number ofthe respective different sequential recurring units, y₁₁ being at leastabout 10, y₁₂ being about one, n being at least about 50 and less thanabout
 100. 57. A polymer of claim 1, wherein said polymer is a formulaIX extended chain crystalline copolymer having the formulas: ##STR1043##wherein a₁ b₁ and a₁ b₂ are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ being between about 0.95 and one, a₁ b₂being equal to 1-a₁ b₁ ; wherein y₁₁ and y₁₂ are the said average numberof the respective different sequential recurring units, y₁₁ being atleast about 20, y₁₂ being about one, n being at least about 50 and lessthan about
 100. 58. A polymer of claim 1, wherein said polymer is aformula IX extended chain crystalline copolymer having the formulas:##STR1044## wherein a₁ b₁ and a₁ b₂ are the said molar proportions ofthe respective different recurring units, a₁ b₁ being between about 0.9and one, a₁ b₂ being equal to 1-a₁ b₁ ; wherein y₁₁ and y₁₂ are the saidaverage number of the respective different sequential recurring units,y₁₁ being at least about 10, y₁₂ being about one, n being at least about50 and less than about
 150. 59. A polymer of claim 1, wherein saidpolymer is a formula IX extended chain crystalline copolymer having theformulas: ##STR1045## wherein c₁ and c₂ are the said molar proportionsof the respective different recurring units, c₁ being between about 0.75and one, c₂ being equal to 1-c₁ ; wherein y₁ and y₂ are the said averagenumber of the respective different sequential recurring units, y₁ beingat least about 4, y₂ being about 1.3, n being at least about 50 and lessthan about
 200. 60. A polymer of claim 1, wherein said polymer is aformula IX extended chain crystalline copolymer having the formulas:##STR1046##
 61. A polymer of claim 1, wherein said polymer is a formulaIX extended chain crystalline copolymer having the formulas: ##STR1047##62. A polymer of claim 1, wherein said polymer is a formula IX extendedchain crystalline copolymer having the formulas: ##STR1048##
 63. Apolymer of claim 1, wherein said polymer is a formula IX extended chaincrystalline copolymer having the formulas: ##STR1049##
 64. A polymer ofclaim 1, wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1050##
 65. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1051##
 66. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1052##
 67. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystallinecopolymer having the formulas: ##STR1053##
 68. A polymer of claim 1,wherein said polymer is an extended chain crystalline block polymerhaving the general formulas: ##STR1054## wherein Ar¹ is ##STR1055## X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ of each heteroring are disposed ortho to one another and Y² is nil or is ##STR1056##a_(i) b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer; ##STR1057##wherein Ar³ is ##STR1058## X₃ is sulfur, oxygen, or NR (R being hydrogenor an organic group), the nitrogen atom and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of each hetero ring are disposed ortho toone another, c_(k) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR1059## wherein Ar¹ is ##STR1060## X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or is ##STR1061## a_(i)b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(ij)represents an average number of the respective different sequentialrecurring units present in said block polymer, Ar³ is ##STR1062## X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atom and X₃ being bonded to aromatic carbon atoms of Ar³ and X₃of each hetero ring are disposed ortho to one another, c_(k) m'/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(k) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR1063## wherein Ar¹ is##STR1064## Ar⁴ is ##STR1065## the nitrogen atoms being bonded to Ar¹and the carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR1066## wherein Ar¹ is##STR1067## when bonded to nitrogen atoms; and when Ar¹ is bonded toboth nitrogen atoms and X₁ and X₂, Ar¹ is ##STR1068## Ar⁴ is ##STR1069##the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y' representsan average number of the respective different sequential recurring unitspresent in said block polymer,X₁ and X₂ are the same or different andare sulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR1070## m/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR1071## wherein Ar³ is ##STR1072## X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atom and X₃ being bonded to aromatic carbon atoms of Ar³, N andX₃ of each hetero ring are disposed ortho to one another, p representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y'/2 represents an average number of therespective different sequential recurring units present in said blockpolymer, Ar¹ is ##STR1073## Ar⁴ is ##STR1074## the nitrogen atoms beingbonded to Ar¹ and the carbon atoms being bonded to Ar⁴, q represents themolar proportions of the respective different recurring units present insaid block polymer, y represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR1075## wherein Ar⁴ is ##STR1076## Ar¹ is##STR1077## and Ar⁵ is ##STR1078## the carbon atoms being bonded to Ar⁴and Ar⁵, and the nitrogen atoms being bonded to Ar¹ and Ar⁵, n being apositive integer; c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer; ##STR1079##wherein Ar¹ is ##STR1080## Ar⁶ is ##STR1081## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₁ and X₂ being bonded to aromatic carbonatoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hetero ring are disposedortho to one another, a_(i) b_(j) represents the molar proportions ofthe respective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; ##STR1082## wherein Ar¹ is ##STR1083## Ar⁶ is##STR1084## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₁ andX₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂of each hetero ring are disposed ortho to one another, a_(i) b_(j)m/m+m' represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer. Ar⁹ is ##STR1085## X₄ is sulfur, oxygen,or NR (R being hydrogen or an organic group), the NH groups and X₄ beingbonded to aromatic carbon atoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y_(k) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; or ##STR1086## wherein Ar¹ is##STR1087## Y⁷ is ##STR1088## the nitrogen atoms being bonded toaromatic carbon atoms of Ar¹ and bonded to adjacent carbon atoms of Y⁷,a_(i) b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 69. A polymerof claim 1, wherein said polymer is an extended chain crystalline blockpolymer having the general formula: ##STR1089## wherein Ar¹ is##STR1090## X₁ and X₂ are the same or different and are sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₁and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ or X₂ ofeach hetero ring are disposed ortho to one another and Y² is nil or is##STR1091## a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.
 70. A polymer of claim 1, wherein said polymer is anextended chain crystalline block polymer having the general formula:##STR1092## wherein Ar³ is ##STR1093## X₃ is sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the nitrogen atom and X₃ beingbonded to aromatic carbon atoms of Ar³, N and X₃ of each hetero ring aredisposed ortho to one another, c_(k) represents the molar proportions ofthe respective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.
 71. A polymer of claim 1, wherein said polymer is anextended chain crystalline block polymer having the general formula:##STR1094## wherein Ar¹ is ##STR1095## X₁ and X₂ are the same ordifferent and are sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₁ and X₂ being bonded to aromatic carbonatoms of Ar¹, N and X₁ or X₂ of each hetero ring are disposed ortho toone another and Y² is nil or is ##STR1096## a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar³ is ##STR1097## X₃ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atom and X₃ being bonded toaromatic carbon atoms of Ar³, N and X₃ of each hetero ring are disposedortho to one another, c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.
 72. A polymer of claim 1, wherein said polymer is anextended chain crystalline block polymer having the general formula:##STR1098## wherein Ar¹ is ##STR1099## Ar⁴ is ##STR1100## the nitrogenatoms being bonded to Ar¹ and the carbon atoms being bonded to Ar⁴,a_(i) b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 73. A polymerof, claim 1, wherein said polymer is an extended chain crystalline blockpolymer having the general formula: ##STR1101## wherein Ar¹ is##STR1102## when bonded to nitrogen atoms; and when Ar¹ is bonded toboth nitrogen atoms and X₁ and X₂, Ar¹ is ##STR1103## Ar⁴ is ##STR1104##the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y' representsan average number of the respective different sequential recurring unitspresent in said block polymer, X₁ and X₂ are the same or different andare sulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or is ##STR1105## m/m+m' represents the molarporportions of the respective different recurring units present in saidblock polymer, y represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer.
 74. A polymer of claim 1, wherein said polymeris an extended chain crystalline block polymer having the generalformula: ##STR1106## wherein Ar³ is ##STR1107## X₃ is sulfur, oxygen, orNR (R being hydrogen or an organic group), the nitrogen atoms and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, p represents the molarproportions of the respective different recurring units present in saidblock polymer, y'/2 represents an average number of the respectivedifferent sequential recurring units present in said block polymer, Ar¹is ##STR1108## Ar⁴ is ##STR1109## the nitrogen atoms being bonded to Ar¹and the carbon atoms being bonded to Ar⁴, q represents the molarproportions of the respective different recurring units present in saidblock polymer, y represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer.
 75. A polymer of claim 1, wherein said polymeris an extended chain crystalline block polymer having the generalformula: ##STR1110## wherein Ar⁴ is ##STR1111## Ar¹ is ##STR1112## andAr⁵ is ##STR1113## the carbon atoms being bonded to Ar⁴ and Ar⁵, and thenitrogen atoms being bonded to Ar¹ and Ar⁵, n being a positive integer;c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, n being a positive integer.
 76. A polymer of claim 1,wherein said polymer is an extended chain crystalline block polymerhaving the general formula: ##STR1114## wherein Ar¹ is ##STR1115## Ar⁶is ##STR1116## X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the NH groups andX₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH andX₁ or X₂ of each hetero ring are disposed ortho to one another, a_(i)b_(j) represents the molar proportions of the respective differentrecurring units present in said block polymer, y_(ij) represents anaverage number of the respective different sequential recurring unitspresent in said block polymer, n being a positive integer.
 77. A polymerof claim 1, wherein said polymer is an extended chain crystalline blockpolymer having the general formula: ##STR1117## wherein Ar¹ is##STR1118## Ar⁶ is ##STR1119## X₁ and X₂ are the same or different andare sulfur, oxygen, or NR (R being hydrogen or an organic group), the NHgroups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶ andAr¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m /m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, Ar⁹ is##STR1120## X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₄ being bonded to aromatic carbon atoms ofAr⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.
 78. A polymer of claim 1, wherein said polymer is anextended chain crystalline block polymer having the general formula:##STR1121## wherein Ar¹ is ##STR1122## Y⁷ is ##STR1123## the nitrogenatoms being bonded to aromatic carbon atoms of Ar¹ and bonded toadjacent carbon atoms of Y⁷, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer.
 79. A polymer of claim 1, wherein said polymeris a formula IX extended chain crystalline block polymer having theformulas: ##STR1124## wherein a₁ b₁, a₁ b₂, a₂ b₁, and a₂ b₂ are thesaid molar proportions of the respective different recurring units, a₁b₁ being between zero and one, a₁ b₂ or a₂ b₁ or a₂ b₂ being equal to1-a₁ b₁ ; wherein y₁₁, y₁₂, y₂₁, and y₂₂ are the said average number ofthe respective different sequential recurring units, y₁₁ being greaterthan about 20 and less than about 75, y₁₂ or y₂₁ or y₂₂ being greaterthan one and less than about 75, n being an average number of totalrecurring units greater than about 50 and less than about
 150. 80. Apolymer of claim 1, wherein said polymer is a formula IX extended chaincrystalline block polymer having the formulas: ##STR1125## wherein a₁ b₁and a₂ b₁ are the said molar proportions of the respective differentrecurring units, a₁ b₁ being between zero and one, a₂ b₁ being equal to1-a₁ b₁ ; wherein y₁₁ and y₂₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 20 and less than about 75, y₂₁ being greater than one and lessthan about 75, n being an average number of total recurring unitsgreater than about 50 and less than about
 150. 81. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1126## wherein a₁ b₁, a₁ b₂ and a₂ b₁are the said molar proportions of the respective different recurringunits, a₁ b₁ being between about 0.5 and one, a₁ b₂ or a₂ b₁ being equalto 1-a₁ b₁ ; wherein y₁₁, y₁₂ and y₂₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 20 and less than about 75, y₁₂ or y₂₁ being greater than one andless than about 75, n being an average number of total recurring unitsgreater than about 50 and less than about
 150. 82. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1127## wherein a₁ b₁, a₁ b₂ and a₂ b₁are the said molar proportions of the respective different recurringunits, a₁ b₁ being between about 0.6 and one, a₁ b₂ or a₂ b₁ being equalto 1-a₁ b₁ ; wherein y₁₁ and y₁₂ or y₂₁ are the said average number ofthe respective different sequential recurring units, y₁₁ being greaterthan about 30, y₁₂ or y₂₁ being greater than one and less than about 50,n being an average number of total recurring units greater than about 50and less than about
 150. 83. A polymer of claim 1, wherein said polymeris a formula XI extended chain crystalline block polymer having theformulas: ##STR1128## wherein c₁ and c₂ are the said molar proportionsof the respective different recurring units, c₁ being between about 0.5and one, c₂ being equal to 1-c₁ ; wherein y₁ and y₂ are the said averagenumber of the respective different sequential recurring units, y₁ beinggreater than about 30 and less than about 100, y₂ being greater than oneand less than about 50, n being an average number of total recurringunits greater than about 60 and less than about
 200. 84. A polymer ofclaim 1, wherein said polymer is a formula X extended chain crystallineblock polymer having the formulas: ##STR1129## wherein a₁ b₁ m/m+m' andc₁ m'/m+m' are the said molar proportions of the respective differentrecurring units, a₁ b₁ m/m+m' being between zero and about 0.5, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than one and less than about 75, y₁ being greater thanabout 30 and less than about 75, n being an average number of totalrecurring units greater than about 75 and less than about
 150. 85. Apolymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1130## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between about 0.5 and one,c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are thesaid average number of the respective different sequential recurringunits, y₁₁ being greater than about 30 and less than about 75, y₁ beinggreater than 5 and less than about 30, n being an average number oftotal recurring units greater than about 60 and less than about
 150. 86.A polymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1131## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between zero and 0.5, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than about one and less than about 75, y₁ beinggreater than about 30 and less than about 75, n being an average numberof total recurring units greater than about 75 and less than about 150.87. A polymer of claim 1, wherein said polymer is a formula X extendedchain crystalline block polymer having the formulas: ##STR1132## whereina₁ b₁ m/m+m' and c₁ m'/m+m' are the said molar proportions of therespective different recurring units, a₁ b₁ m/m+m' being between about0.5 and one, c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ andy₁ are the said average number of the respective different sequentialrecurring units, y₁₁ being greater than about 30 and less than about 75,y₁ being greater than 5 and less than about 30, n being an averagenumber of total recurring units greater than about 60 and less thanabout
 150. 88. A polymer of claim 1, wherein said polymer is a formula Xextended chain crystalline block polymer having the formulas:##STR1133## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between zero and 0.5, c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m';wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about oneand less than about 75, y₁ being greater than about 30 and less thanabout 75, n being an average number of total recurring units greaterthan about 75 and less than about
 150. 89. A polymer of claim 1, whereinsaid polymer is a formula X extended chain crystalline block polymerhaving the formulas: ##STR1134## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' arethe said molar proportions of the respective different recurring units,a₁ b₁ m/m+m' being between about 0.5 and one, c₁ m'/m+m' being equal to1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout 30 and less than about 75, y₁ being greater than 5 and less thanabout 30, n being an average number of total recurring units greaterthan about 60 and less than about
 150. 90. A polymer of claim 1, whereinsaid polymer is a formula X extended chain crystalline block polymerhaving the formulas: ##STR1135## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' arethe said molar proportions of the respective different recurring units,a₁ b₁ m/m+m' being between zero and about 0.5, c₁ m'/m+m' being equal to1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the said average number of therespective different sequential recurring units, y₁₁ being greater thanabout one and less than about 75, y₁ being greater than about 30 andless than about 75, n being an average number of total recurring unitsgreater than about 75 and less than about
 150. 91. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1136## wherein a₁ b₁ m/m+m' and c₁m'/m+m' are the said molar proportions of the respective differentrecurring units, a₁ b₁ m/m+m' being between about 0.5 and one, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than about 30 and less than about 75, y₁ being greaterthan 5 and less than about 30, n being an average number of totalrecurring units greater than about 60 and less than about
 150. 92. Apolymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1137## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between about 0.5 and one,c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are thesaid average number of the respective different sequential recurringunits, y₁₁ being greater than about 30 and less than about 75, y₁ beinggreater than 5 and less than about 30, n being an average number oftotal recurring units greater than about 60 and less than about
 150. 93.A polymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1138## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between about 0.5 and one,c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are thesaid average number of the respective different sequential recurringunits, y₁₁ being greater than about 30 and less than about 75, y₁ beinggreater than 5 and less than about 30, n being an average number oftotal recurring units greater than about 60 and less than about
 150. 94.A polymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1139## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between about 0.5 and one,c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are thesaid average number of the respective different sequential recurringunits, y₁₁ being greater than about 30 and less than about 75, y₁ beinggreater than 5 and less than about 30, n being an average number oftotal recurring units greater than about 60 and less than about
 150. 95.A polymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1140## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between zero and one, c₁m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ are the saidaverage number of the respective different sequential recurring units,y₁₁ being greater than about one, y₁ being greater than about 5, n beingan average number of total recurring units greater than about 50 andless than about
 200. 96. A polymer of claim 1, wherein said polymer is aformula X extended chain crystalline block polymer having the formulas:##STR1141## wherein a₁ b₁ m/m+m' and c₁ m'/m+m' are the said molarproportions of the respective different recurring units, a₁ b₁ m/m+m'being between zero and one, c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m';wherein y₁₁ and y₁ are the said average number of the respectivedifferent sequential recurring units, y₁₁ being greater than about one,y₁ being greater than about 5, n being an average number of totalrecurring units greater than about 50 and less than about
 200. 97. Apolymer of claim 1, wherein said polymer is a formula X extended chaincrystalline block polymer having the formulas: ##STR1142## wherein a₁ b₁m/m+m' and c₁ m'/m+m' are the said molar proportions of the respectivedifferent recurring units, a₁ b₁ m/m+m' being between zero and about0.5, c₁ m'/m+m' being equal to 1-a₁ b₁ m/m+m'; wherein y₁₁ and y₁ arethe said average number of the respective different sequential recurringunits, y₁₁ being greater than about one and less than about 20, y₁ beinggreater than about 30, n being an average number of total recurringunits greater than about 75 and less than about
 150. 98. A polymer ofclaim 1, wherein said polymer is a formula XI extended chain crystallineblock polymer having the formulas: ##STR1143##
 99. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1144##
 100. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1145##
 101. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1146##
 102. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1147##
 103. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1148##
 104. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1149##
 105. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1150##
 106. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1151##
 107. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1152##
 108. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1153##
 109. A polymer of claim 1,wherein said polymer is a formula IX extended chain crystalline blockpolymer having the formulas: ##STR1154##
 110. A polymer of claim 1,wherein said polymer is a formula XI extended chain crystalline blockpolymer having the formulas: ##STR1155##
 111. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1156##
 112. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1157##
 113. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1158##
 114. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1159##
 115. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1160##
 116. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1161##
 117. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1162##
 118. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1163##
 119. A polymer of claim 1,wherein said polymer is a formula X extended chain crystalline blockpolymer having the formulas: ##STR1164##
 120. A process for preparing aliquid crystalline extended chain polymer composition of workableviscosity which is useful in the production of fibers and filmscomprising the following steps:(a) mixing at least one of a selectedfirst homo- or hetero- bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide afirst mixture of the first monomer(s) in the preliminary solvent, (c)adding at least one of a selected second monomer in the resultingmixture of step (b) when said selected first monomer is ahomo-bifunctional monomer so as to provide a first mixture of the firstand second monomers in the preliminary solvent, (d) then increasing thephosphorus pentoxide content of the mixture resulting from step (b) or(c) to provide a first or a first and second monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (e) causingpolymerization of the first or the first and second monomer(s) at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product or a first co-oligomeric product having apreselected intrinsic viscosity, or (f) causing polymerization of thefirst or the first and second monomer(s) at a temperature sufficient toeffect reaction at a rate to form a first homo-polymeric product or afirst copolymeric product, (g) mixing a selected amount of the firsthomo-oligomeric product with a selected amount of at least one of aselected second homo-oligomeric product so as to form a firstpoly-oligomeric product, said second homo-oligomeric product beingformed by like steps (a) and (b) followed by:(1g) adding at least one ofa selected second monomer in the resulting mixture of step (b) when saidselected first monomer is a homo-bifunctional monomer so as to provide amixture of a first and second monomer in the preliminary solvent, (2g)then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (1g) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization, (3g) causing polymerization of the first or firstand second monomer(s) at a temperature sufficient to effect reaction ata rate to form said second homo-oligomeric product having a preselectedintrinsic viscosity, with the overall proviso that at least one of theselected monomer(s) of step (a) or (1g) which forms the secondhomo-oligomeric product be different from at least one of the selectedmonomer(s) of step (a) or (c) which forms the first homo-oligomericproduct, or (h) mixing a selected amount of the first homo-oligomericproduct with a selected amount of a second mixture of at least one of aselected first monomer or a first and second monomer in the preliminarysolvent so as to form a monomer-oligomer mixture, and then increasingthe phosphorus pentoxide content of said monomer-oligomer mixture toprovide a monomer-oligomer reaction medium of greater phosphoruspentoxide content suitable for polymerization, said first monomer ofsaid second mixture being formed by like steps (a) and (b) and saidfirst and second monomer of said second mixture being formed by likesteps (a), (b) and (c), with the overall proviso that at least one ofthe selected monomer of step (a) or (c) which forms the first or firstand second monomer(s) of said second mixture, be different from at leastone of the selected monomer(s) of step (a) or (c) which forms the firsthomo-oligomeric product, (i) causing polymerization of thepoly-oligomeric product resulting from step (g) or the monomer-oligomerresulting from step (h) at a temperature sufficient to effect reactionat a rate to form a first block-oligomeric product having a preselectedintrinsic viscosity or a first blockpolymeric product.
 121. A processfor preparing a liquid crystalline extended chain polymer composition ofworkable viscosity which is useful in the production of fibers and filmscomprising the following steps:(a) preparing a reaction medium suitablefor polymerization, said reaction medium comprising at least one of aselected monomer and polyphosphoric acid; and (b) causing polymerizationof said monomer;said step (a) being conducted substantially within theshaded phosphorus pentoxide content profile area bounded by ABCGHI ofFIG. 14; and said step (b) being conducted substantially within theshaded phosphorus pentoxide content profile area bounded by DCGFE ofFIG.
 14. 122. A process according to claim 121, wherein a selectedweight in grams, a* of said preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, m_(o), is added inaccordance with the empirical equation:

    a*={[1-f]([P.sub.y /P.sub.c ]-P.sub.y)-[n.sub.o (18.02)/M.sub.w ]P.sub.y }(1-m.sub.o).sup.-1

where P_(y) =weight in grams of a predetermined theoretical yield ofsaid extended chain homopolymer, copolymer, or blockpolymer; P_(c)=preselected weight fraction of said extended chain homopolymer,copolymer, or blockpolymer of the total weight of said firsthomopolymeric product, said first copolymeric product, or said firstblock-polymeric product following polymerization; n_(o) =integer numberof moles of polycondensation by-product per moles of repeating unit ofsaid extended chain homopolymer, copolymer, or blockpolymer;18.02=molecular weight of polycondensation by-product; M_(w) =molecularweight of said extended chain homopolymer, copolymer, or blockpolymerrecurring unit; and f=preselected phosphorus pentoxide content of saidfirst homo-oligomeric product, said first co-oligomeric product, saidfirst homopolymeric product, said first copolymeric product, said secondhomo-oligomeric product, said second co-oligomeric product, saidpoly-oligomeric product, said first block-oligomeric product or saidfirst block-polymeric product,said f being achieved by incorporating aselected intermediate weight in grams, b* of phosphorus pentoxide insaid increasing phosphorus pentoxide content step forming said firstmonomer reaction medium, said first and second monomer reaction medium,said monomer-oligomer reaction medium, or said first oligomer-monomerreaction medium of greater phosphorus pentoxide content in accordancewith the empirical equation:

    b*=[P.sub.y /P.sub.c ]-P.sub.y -[{n.sub.o (18.02)/M.sub.w }[P.sub.y -a*.


123. A process for preparing a liquid crystalline extended chainhomopolymer composition of workable viscosity which is useful in theproduction of fibers and films comprising the following steps:(a) mixinga selected first homo- or hetero- bifunctional monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a first mixture of the first monomer in the preliminarysolvent, (c) adding a selected second monomer to the resulting mixtureof step (b) when said selected first monomer is a homo-bifunctionalmonomer so as to provide a first mixture of the first and second monomerin the preliminary solvent, (d) then increasing the phosphorus pentoxidecontent of the mixture resulting from step (b) or (c) to provide a firstor a first and second monomer reaction medium of greater phosphoruspentoxide content suitable for polymerization and for achieving a degreeof polymerization greater than about 40, (e) causing polymerization ofthe first or the first and second monomer(s) at a temperature sufficientto effect reaction at a rate to form a first homo-oligomeric producthaving a preselected intrinsic viscosity, or (f) causing polymerizationof the first or the first and second monomer(s) at a temperaturesufficient to effect reaction at a rate to form a first homopolymericproduct.
 124. A process according to claim 120 wherein said stepscomprises:(a) mixing at least one of a selected first homo- or hetero-bifunctional monomer with or without oxidation protecting atoms orgroups with a preliminary solvent of phosphoric acid having a relativelylow phosphorus pentoxide content, (b) heating and optionally placing theresulting mixture under reduced pressure to remove any volatilizedprotecting atoms or groups present and provide a first mixture of thefirst monomer(s) in the preliminary solvent, (c) adding at least one ofa selected second monomer in the resulting mixtue of step (b) when saidselected first monomer is a homo- bifunctional monomer so as to providea first mixture of the first and second monomer in the preliminarysolvent, (d) then increasing the phosphorus pentoxide content of themixture resulting from step (b) or (c) to provide a first or a first andsecond monomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization and for achieving a degree of polymerizationgreater than about 40, (e) causing polymerization of the first or thefirst and second monomer(s) at a temperature sufficient to effectreaction at a rate to form a first co-oligomeric product having apreselected intrinsic viscosity, or (f) causing polymerization of thefirst or the first and second monomer(s) at a temperature sufficient toeffect reaction at a rate to form a first copolymeric product.
 125. Aprocess for preparing a liquid crystalline extended chain block polymercomposition of workable viscosity which is useful in the production offibers and films comprising the following steps:(a) mixing at least oneof a selected first homo- or hetero-bifunctional monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a first mixture of the first monomer in the preliminarysolvent, (c) adding at least one of a selected second monomer to theresulting mixture of step (b) when said selected first monomer is ahomo-bifunctional monomer so as to provide a first mixture of the firstand second monomers in the preliminary solvent, (d) then increasing thephosphorus pentoxide content of the mixture resulting from step (b) or(c) to provide a first or a first and second monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (e) causingpolymerization of the first or the first and second monomer at atemperature sufficient to effect reaction at a ratio to form a firsthomo-oligomeric product or a first co-oligomeric product having apreselected intrinsic viscosity, or (f) mixing a selected amount of thefirst homo-oligomeric product with a selected amount of at least one ofa selected second homo-oligomeric product so as to form a firstpoly-oligomeric product, said second homo-oligomeric product beingformed by like steps (a) and (b) followed by:(1f) adding at least one ofa selected second monomer in the resulting mixture of step (b) when saidselected first monomer is a homo-bifunctional monomer so as to provide amixture of a first and second monomer in the preliminary solvent, (2f)then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (1f) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization, (3f) causing polymerization of the first or firstand second monomer(s) at a temperature sufficient to effect reaction ata rate to form said second homo-oligomeric product having a preselectedintrinsic viscosity, with the overall proviso that at least one of theselected monomer of step (a) or (1f) which forms the secondhomo-oligomeric product be different from at least one of the selectedmonomer of step (a) or (c) which forms the first homo-oligomericproduct, or (g) mixing a selected amount of the first homo-oligomericproduct with a selected amount of a second mixture of at least one of aselected first monomer or a first and second monomer in the preliminarysolvent so as to form a monomer-oligomer mixture, and then increasingthe phosphorus pentoxide content of said monomer-oligomer mixture toprovide a monomer-oligomer reaction medium of greater phosphoruspentoxide content suitable for polymerization, said first monomer ofsaid second mixture being formed by like steps (a) and (b) and saidfirst and second monomer of said second mixture being formed by likesteps (a), (b) and (c), with the overall proviso that at least one ofthe selected monomer of step (a) or (c) which forms the first or firstand second monomer of said second mixture, be different from at leastone of the selected monomer of step (a) or (c) which forms the firsthomo-oligomeric product, (h) causing polymerization of thepoly-oligomeric product resulting from step (f) or the monomer-oligomerresulting from step (g) at a temperature sufficient to effect reactionat a rate to form a first block-oligomeric product having a preselectedintrinsic viscosity or a first block-polymeric product.
 126. A processaccording to claim 120 wherein said steps comprises:(a) mixing aselected first hetero-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomer in the preliminary solvent, (c) thenincreasing the phosphorus pentoxide content of the mixture resultingfrom step (b) to provide a first monomer reaction medium of greaterphosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (d) causingpolymerization of the first monomer at a temperature sufficient toeffect reaction at a rate to form a first homo-oligomeric product havinga preselected intrinsic viscosity or a first homopolymeric product. 127.A process for preparing a liquid crystalline extended chain homopolymercomposition of workable viscosity which is useful in the production offibers and films comprising the following steps:(a) mixing a selectedfirst homo-bifunctional monomer with or without oxidation protectingatoms or groups with a preliminary solvent of phosphoric acid having arelatively low phosphorus pentoxide content, (b) heating and optionallyplacing the resulting mixture under reduced pressure to remove anyvolatilized protecting atoms or groups present and provide a mixture ofthe first monomer in the preliminary solvent, (c) adding a selectedsecond monomer in the resulting mixture of step (b) to provide a mixtureof the first and second monomer in the preliminary solvent, (d) thenincreasing the phosphorus pentoxide content of the mixture resultingfrom step (c) to provide a first and second monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (e) causingpolymerization of the first and second monomers at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity or a firsthomopolymeric product.
 128. A process according to claim 120 whereinsaid steps comprises:(a) mixing at least two of a selected firsthomo-bifunctional monomers with or without oxidation protecting atoms orgroups with a preliminary solvent of phosphoric acid having a relativelylow phosphorus pentoxide content, (b) heating and optionally placing theresulting mixture under reduced pressure to remove any volatilizedprotecting atoms or groups present and provide a mixture of the firstmonomer in the preliminary solvent, (c) adding at least one of selectedsecond monomer in the resulting mixture of step (b) to provide a mixtureof the first and second monomeers in the preliminary solvent, (d) thenincreasing the phosphorus pentoxide content of the mixture resultingfrom step (c) to provide a first and second monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization, (e)causing polymerization of the first and second monomers at a temperaturesufficient to effect reaction at a rate to form a first co-oligomericproduct having a preselected intrinsic viscosity or a first copolymericproduct.
 129. A process according to claim 120 wherein said stepscomprises:(a) mixing at least one of a selected first homo-bifunctionalmonomer with a without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content, (b) heating and optionally placing theresulting mixture under reduced pressure to remove any volatilizedprotecting atoms or groups present and provide a mixture of the firstmonomer(s) in the preliminary solvent, (c) adding at least two of aselected second monomers in the resulting mixture of step (b) to providea mixture of the first and second monomers in the preliminary solvent,(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization and for achieving a degree of polymerization greater thanabout 40, (e) causing polymerization of the first and second monomers ata temperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.
 130. A process according to claim 120 whereinsaid steps comprises:(a) mixing at least two of a selected firsthetero-bifunctional monomers with or without oxidation protecting atomsor groups with a preliminary solvent of phosphoric acid having arelatively low phosphorus pentoxide content, (b) heating and optionallyplacing the resulting mixture under reduced pressure to remove anyvolatilized protecting atoms or groups present and provide a mixture ofthe first monomers in the preliminary solvent, (c) then increasing thephosphorus pentoxide content of the mixture resulting from step (b) toprovide a first monomer reaction medium of greater phosphorus pentoxidecontent suitable for polymerization and for achieving a degree ofpolymerization greater than about 40, (d) causing polymerization of thefirst monomers at a temperature sufficient to effect reaction at a rateto form a first co-oligomeric product having a preselected intrinsicviscosity or a first copolymeric product.
 131. A process according toclaim 120 wherein said steps comprises:(a) mixing at least one of aselected first hetero-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomer(s) in the preliminary solvent, (c) thenincreasing the phosphorus pentoxide content of the mixture resultingfrom step (b) to provide a first monomer reaction medium of greaterphosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (d) causingpolymerization of the first monomer(s) at a temperature sufficient toeffect reaction at a rate to form a first homo- or co-oligomeric producthaving a preselected intrinsic viscosity, (e) mixing a selected amountof the first homo- or co-oligomeric product with a selected amount of aselected second homo- or co-oligomeric product so as to form a firstpoly-oligomeric product, said second homo- or co-oligomeric productbeing formed by like steps (a), (b), (c), and (d) with the overallproviso that at least one of the selected monomer of step (a) whichforms the second homo- or co-oligomeric product be different from theselected monomer of step (a) which forms the first homo- orco-oligomeric product, (f) causing polymerization of the poyl-oligomericproduct at a temperature sufficient to effect reaction at a rate to forma first block-oligomeric product having a preselected intrinsicviscosity or a first blockpolymeric product.
 132. A process forpreparing a liquid crystalline extended chain block polymer compositionof workable viscosity which is useful in the production of fibers andfilms comprising the following steps:(a) mixing at least one of aselected first homo-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomers in the preliminary solvent, (c) adding atleast one of a selected second monomer in the resulting mixture of step(b) to provide a mixture of the first and second monomers in thepreliminary solvent, (d) then increasing the phosphorus pentoxidecontent of the mixture resulting from step (c) to provide a first andsecond monomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization and for achieving a degree of polymerizationgreater than about 40, (e) causing polymerization of the first andsecond monomers at a temperature sufficient to effect reaction at a rateto form a first homo- or co-oligomeric product having a preselectedintrinsic viscosity, (f) mixing a selected amount of the first homo- orco-oligomeric product with a selected amount of at least one of aselected second homo- or co-oligomeric product so as to form a firstpoly-oligomeric product, said second homo- or co-oligomeric productbeing formed by like steps (a), (b), (c), (d), and (e) with the overallproviso that at least one of the selected monomer of step (a) or (c)which forms the second homo-oligomeric product be different from atleast one of the selected monomer of step (a) or (c) which forms thefirst homo-oligomeric product, (g) causing polymerization of thepoly-oligomeric product at a temperature sufficient to effect reactionat a rate to form a first block-oligomeric product having a preselectedintrinsic viscosity or a first blockpolymeric product.
 133. A processfor preparing a liquid crystalline extended chain block polymercomposition of workable viscosity which is useful in the production offibers and films comprising the following steps:(a) mixing at least oneof a selected first homo-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomer(s) in the preliminary solvent, (c) addingat least one of a selected second monomer to the resulting mixture ofstep (b) to provide a first mixture of the first and second monomers inthe preliminary solvent, (d) then increasing the phosphorus pentoxidecontent of the mixture resulting from step (c) to provide a first andsecond monomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization and for achieving a degree of polymerizationgreater than about 40, (e) causing polymerization of the first andsecond monomers at a temperature sufficient to effect reaction at a rateto form a first homo-oligomeric product having a preselected intrinsicviscosity, (f) mixing a selected amount of the first homo-oligomericproduct with a selected amount of a second mixture of a different firstand second monomer in the preliminary solvent, said second mixture beingformed by like steps (a), (b) and (c) with the overall proviso that atleast one of the selected monomers of step (a) or (c) which forms thesecond mixture be different from at least one of the selected monomersof step (a) or (c) which forms the first homo-oligomeric product, (g)then increasing the phosphorus pentoxide content of the mixtureresulting from step (f) to provide a first oligomer-monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization, (h) causing polymerization of the mixture resulting fromstep (g) at a temperature sufficient to effect reaction at a rate toform a first block-oligomeric product having a preselected intrinsicviscosity or a first blockpolymeric product.
 134. A process forpreparing a liquid crystalline extended chain block polymer compositionof workable viscosity which is useful in the production of fibers andfilms comprising the following steps:(a) mixing at least one of aselected first hetero-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomer(s) in the preliminary solvent, (c) thenincreasing the phosphorus pentoxide content of the mixture resultingfrom step (b) to provide a first monomer reaction medium of greaterphosphorus pentoxide content suitable for polymerization and forachieving a degree of polymerization greater than about 40, (d) causingpolymerization of the first monomer at a temperature sufficient toeffect reaction at a rate to form a first homo- or co-oligomeric producthaving a preselected intrinsic viscosity, (e) mixing a selected amountof the first homo- or co-oligomeric product with a selected amount of atleast one of a selected second homo- or co-oligomeric product so as toform a first poly-oligomeric product, said second homo- or co-oligomericproduct being formed by like steps (a) (with the proviso that theselected first monomer is a homo-bifunctional monomer) and (b) followedby:(1e) adding at least one of a selected second monomer in theresulting mixture of step (b) to provide a mixture of a first and secondmonomers in the preliminary solvent, (2e) then increasing the phosphoruspentoxide content of the mixture resulting from step (1e) to provide afirst and second monomer reaction medium of greater phosphorus pentoxidecontent suitable for polymerization and for achieving a degree ofpolymerization greater than about 40, (3e) causing polymerization of thefirst and second monomers at a temperature sufficient to effect reactionat a rate to form said second homo- or co-oligomeric product having apreselected intrinsic viscosity, with the overall proviso that at leastone of the selected monomers of step (a) or (1e) which forms the secondhomo- or co-oligomeric product be different from at least one of theselected monomers of step (a) which forms the first homo- orco-oligomeric product, (f) causing polymerization of the poly-oligomericproduct at a temperature sufficient to effect reaction at a rate to forma first block-oligomeric product having a preselected intrinsicviscosity or a first blockpolymeric product.
 135. A process forpreparing a liquid crystalline extended chain block polymer compositionof workable viscosity which is useful in the production of fibers andfilms comprising the following steps:(a) mixing at least one of aselected first hetero-bifunctional monomer with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content, (b) heating andoptionally placing the resulting mixture under reduced pressure toremove any volatilized protecting atoms or groups present and provide amixture of the first monomer(s) in the preliminary solvent, (c) mixing aselected amount of the mixture of step (b) with a selected amount of atleast one of a selected first homo-oligomeric product so as to form afirst oligomeric-first monomer reaction medium, said firsthomo-oligomeric product being formed by like steps (a) with the provisothat the selected first monomer is a homo-bifunctional monomer) and (b)followed by:(1c) adding at least one of a selected second monomer to theresulting mixture of step (b) to provide a mixture of a first and secondmonomer in the preliminary solvent, (2c) then increasing the phosphoruspentoxide content of the mixture resulting from step (1c) to provide afirst and second monomer reaction medium of greater phosphorus pentoxidecontent suitable for polymerization and for achieving a degree ofpolymerization greater than about 40, (3c) causing polymerization of thefirst and second monomers at a temperature sufficient to effect reactionat a rate to form said first homo-oligomeric product having apreselected intrinsic viscosity, (d) then increasing the phosphoruspentoxide content of the mixture resulting from step (c) to provide areaction medium of greater phosphorus pentoxide content suitable forpolymerization and for achieving a degree of polymerization greater thanabout 40, (e) causing polymerization of the first oligomer-monomer at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst blockpolymeric product.
 136. A process according to claim 120,123, 126 or 127 wherein said selected first monomer is selected from thegroup consisting of:2,5-diamino-1,4-benzenedithiol dihydrochloride,4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzenetetrahydrochloride, 3,3'-dimercaptobenzidine dihydrochloride,3,3'-dihydroxybenzidine dihydrochloride,3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride,3,3'-diaminobenzidine tetrahydrochloride dihydrate,2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochloride,3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoicacid hydrochloride, 4,5 -diaminonaphthalene-1,8-dicarboxylic anhydride,2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene,2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline, or2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride.
 137. A processaccording to claim 120, 123, or 127 wherein said selected second monomeris selected from the group consisting of:terephthalic acid,terephthaloyl chloride, terephthalonitrile, ortrans-1,4-cyclohexanedicarboxylic acid.
 138. A process according toclaim 120, 124, 128, 129, or 130 wherein said selected first monomer isselected from the group consisting of:2,5-diamino-1,4-benzenedithioldihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride,1,2,4,5-tetraaminobenzene tetrahydrochloride, 3,3'dimercaptobenzidinedihydrochloride, 3,3'-dihydroxybenzidine dihydrochloride,3,3'-diamino-4,4'dihydroxybiphenyl dihydrochloride,3,3'-diaminobenzidine tetrahydrochloride dihydrate,2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochoride,3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoicacid hydrochloride, 3,3'-dimercapto-4,4'-diaminodiphenyl etherdihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride,3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 2,3,5,6-tetraaminopyridinetrihydrochloride, 1,5-diamino-2,6-naphthalenedithiol dihydrochloride,1,5-diamino-2,6-naphthalenediol dihydrochloride,1,2,5,6-tetraminonaphthalene tetrahydrochloride,3,3'-dimercapto-4,4'diaminodiphenyl ether dihydrochloride,3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride,3,3'-dihydroxy-4,4'-diaminodiphenyl ether,3,3'-diamino-4,4'dihydroxydiphenyl ether, 3,3',4,4'-tetraaminodiphenylsulfone, 3,3'-dimercapto-4,4'-diaminodiphenyl sulfone,3,3'-diamino-4,4'dihydroxydiphenyl sulfone,3,3',4,4'-tetraaminobenzophenone, 3,6-diamino-1,2-benzenedithioldihydrochloride, 3-mercapto-4-aminobenzoic acid hydrochloride,3-mercapto-4-aminobenzoic acid, or 3,4-diaminobenzoic acid.
 139. Aprocess according to claim 120, 124, 128, or 129, wherein said selectedsecond monomer is selected from the group consisting of:terephthalicacid, terephthaloyl chloride, terephthalonitrile,trans-1,4-cyclohexanedicarboxylic acid, 2,5-pyridinedicarboxylic acid,4,4'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid chloride,2,6-naphthalenedicarboxylic acid, 3,3'-biphenyldicarboxylic acid,trans-1,2-cyclohexanedicarboxylic acid,1,4-bis(5-carboxybenzoxazole-2-yl) benzene2,5-bis(6-carboxybenzothiazole-2-yl)pyridine, isophthalic acid,4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenyl ether, succinicacid, glutaric acid, adipic acid, pimelic acid, sebacic acid,pyromellitic dianhydride, or 1,4,5,8-naphthalenetetracarboxylicdianhydride.
 140. A process according to claim 120, 125, 131, 132, 133,134, or 135 wherein said selected first monomer is selected from thegroup consisting of:2,5-diamino-1,4-benzenedithiol dihydrochloride,4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzenetetrahydrochloride, 3,3'-dimercaptobenzidine dihydrochloride,3,3'-dihydroxybenzidine dihydrochloride,3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride,3,3'-diaminobenzidine tetrahydrochloride dihydrate,2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochloride,3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoicacid hydrochloride, 4,5-diaminonaphthalene-1,8-dicarboxylic anhydride,2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene,2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline, 3-mercapto-4-aminobenzoicacid hydrochloride, 3-mercapto-4-aminobenzoic acid, or2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride.
 141. A processaccording to claim 120, 125, 132, 133, 134, or 135 wherein said selectedsecond monomer is selected from the group consisting of:terephthalicacid, terephthaloyl chloride, or trans-1,4-cyclohexanedicarboxylic acid.142. A process according to claim 120, 125, 131, 132, 133, 134, or 135wherein said selected first monomer of said second homo-oligomericproduct is selected from the group consistingof:2,5-diamino-1,4-benzenedithiol dihydrochloride,4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzenetetrahydrochloride, 3,3'-dimercaptobenzidine dihydrochloride,3,3'-dihydroxybenzidine dihydrochloride,3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride,3,3'-diaminobenzidine tetrahydrochloride dihydrate,2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochloride,3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoicacid hydrochloride, 3,3'-dimercapto-4,4'-diaminodiphenyl etherdihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride,3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 2,3,5,6-tetraaminopyridinetrihydrochloride, 1,5-diamino-2,6-naphthalenedithiol dihydrochloride,1,5-diamino-2,6-naphthalenediol dihydrochloride,1,2,5,6-tetraminonaphthalene tetrahydrochloride,3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride,3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride,3,3'-dihydroxy-4,4'-diaminodiphenyl ether,3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3',4,4'-tetraaminodiphenylsulfone, 3,3'-dimercapto-4,4'-diaminodiphenyl sulfone,3,3'-diamino-4,4'-dihydroxydiphenyl sulfone,3,3',4,4'-tetraaminobenzophenone, 3,6-diamino-1,2-benzenedithioldihydrochloride, 3-mercapto-4-aminobenzoic acid hydrochloride,3-mercapto-4-aminobenzoic acid, or 3,4-diaminobenzoic acid.
 143. Aprocess according to claim 120, 125, 132, 133, 134, or 135 wherein saidselected second monomer of said second homo-oligomeric product isselected from the group consisting of:terephthalic acid, terephthaloylchloride, trans-1,4-cyclohexanedicarboxylic acid,2,5-pyridinedicarboxylic acid, 4,4'-biphenyldicarboxylic acid,4,4'-biphenyldicarboxylic acid chloride, 2,6-naphthalenedicarboxylicacid, 3,3'-biphenyldicarboxylic acid, trans-1,2-cyclohexanedicarboxylicacid, 1,4-bis(5-carboxybenzoxazole-2-yl)benzene,2,5-bis(6-carboxybenzothiazole-2yl)pyridine, isophthalic acid,4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenyl ether, succinicacid, glutaric acid, adipic acid, pimelic acid, sebacic acid,pyromellitic dianhydride, or 1,4,5,8-naphthalenetetracarboxylicdianhydride.
 144. A process according to claim 120, 127, 128, 129, 132,133, 134, or 135 wherein said selected first monomer is2,5-diamino-1,4-benzenedithiol dihydrochloride or4,6-diamino-1,3-benzenediol dihydrochloride.
 145. A process according toclaim 120, 123, 124, 125, 126, 130, 131, 134, or 135 wherein saidselected first monomer is 3-amino-4-hydroxy benzoic acid hydrochlorideor 3-mercapto-4-aminobenzoic acid hydrochloride.
 146. A processaccording to claim 120, 123, 124, 125, 126, 127, 128, 129, 130, 131,132, 133, 134, or 135 wherein said phosphorus pentoxide in saidpreliminary solvent is present in an amount below about 77% by weight.147. A process according to claim 136 wherein said phosphorus pentoxidein said preliminary solvent is present in an amount below about 77% byweight.
 148. A process according to claim 137 wherein said phosphoruspentoxide in said preliminary solvent is present in an amount belowabout 77% by weight.
 149. A process according to claim 138 wherein saidphosphorus pentoxide in said preliminary solvent is present in an amountbelow about 77% by weight.
 150. A process according to claim 139 whereinsaid phosphorus pentoxide in said preliminary solvant is present in anamount below about 77% by weight.
 151. A process according to claim 140wherein said phosphorus pentoxide in said preliminary solvent is presentin an amount below about 77% by weight.
 152. A process according toclaim 141 wherein said phosphorus pentoxide in said preliminary solventis present in an amount below about 77% by weight.
 153. A processaccording to claim 142 wherein said phosphorus pentoxide in saidpreliminary solvent is present in an amount below about 77% by weight.154. A process according to claim 143 wherein said phosphorus pentoxidein said preliminary solvent is present in an amount below about 77% byweight.
 155. A process according to claim 144 wherein said phosphoruspentoxide in said preliminary solvent is present in an amount belowabout 77% by weight.
 156. A process according to claim 145 wherein saidphosphorus pentoxide in said preliminary solvent is present in an amountbelow about 77% by weight.
 157. A process according to claim 120, 123,124, 126, 127, 128, 129, 130, 131, 132, 133, 135 or 121 wherein saidpolymerization reaction is conducted at a temperature of from about 100°C. to greater than about 160° C. and at a polymerization time of fromabout 2 hours to about 8 hours.
 158. A process according to claim 120,123, 124, 126, 127, 128, 129, 130, 131, 132, 133, 134, or 135 whereinsaid phosphorus pentoxide content of said first homo-oligomeric product,said first co-oligomeric product, said second homo-oligomeric product,said second co-oligomeric product, said first block-oligomeric product,or said first blockpolymeric product formed by said polymerizationreaction is between about 82% and about 84% by weight.
 159. A processaccording to claim 136 wherein said phosphorus pentoxide content of saidfirst homo-oligomeric product, said first co-oligomeric product, saidsecond homo-oligomeric product, said second co-oligomeric product, saidfirst block-oligomeric product, or said first blockpolymeric productformed by said polymerization reaction is between about 82% and about84% by weight.
 160. A process according to claim 137 wherein saidphosphorus pentoxide content of said first homo-oligomeric product, saidfirst co-oligomeric product, said second homo-oligomeric product, saidsecond co-oligomeric product, said first block-oligomeric product, orsaid first blockpolymeric product formed by said polymerization reactionis between about 82% and about 84% by weight.
 161. A process accordingto claim 138 wherein said phosphorus pentoxide content of said firsthomo-oligomeric product, said first co-oligomeric product, said secondhomo-oligomeric product, said second co-oligomeric product, said firstblock-oligomeric product, or said first blockpolymeric product formed bysaid polymerization reaction is between about 82% and about 84% byweight.
 162. A process according to claim 139 wherein said phosphoruspentoxide content of said first homo-oligomeric product, said firstco-oligomeric product, said second homo-oligomeric product, said secondco-oligomeric product, said first block-oligomeric product, or saidfirst blockpolymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 163. A process according toclaim 140 wherein said phosphorus pentoxide content of said firsthomo-oligomeric product, said first co-oligomeric product, said secondhomo-oligomeric product, said second co-oligomeric product, said firstblock-oligomeric product, or said first blockpolymeric product formed bysaid polymerization reaction is between about 82% and about 84% byweight.
 164. A process according to claim 141 wherein said phosphoruspentoxide content of said first homo-oligomeric product, said firstco-oligomeric product, said second homo-oligomeric product, said secondco-oligomeric product, said first block-oligomeric product, or saidfirst blockpolymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 165. A process according toclaim 142 wherein said phosphorus pentoxide content of said firsthome-olibomeric product, said first co-oligomeric product, said secondhomo-oligomeric product, said second co-oligomeric product, said firstblock-oligomeric product, or said first blockpolymeric product formed bysaid polymerization reaction is between about 82% and about 84% byweight.
 166. A process according to claim 143 wherein said phosphoruspentoxide content of said first homo-oligomeric product, said firstco-oligomeric product, said second homo-oligomeric product, said secondco-oligomeric product, said first block-oligomeric product, or saidfirst blockpolymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 167. A process according toclaim 144 wherein said phosphorus pentoxide content of said firsthomo-oligomeric product, said first co-oligomeric product, said secondhomo-oligomeric product, said second co-oligomeric product, said firstblock-oligomeric product, or said first blockpolymeric product formed bysaid polymerization reaction is between about 82% and about 84% byweight.
 168. A process according to claim 145 wherein said phosphoruspentoxide content of said first homo-oligomeric product, said firstco-oligomeric product, said second homo-oligomeric product, said secondco-oligomeric product, said first block-oligomeric product, or saidfirst blockpolymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 169. A process according toclaim 120, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134,135, or 121 wherein said polymerization reaction is conducted at atemperature within the range of from about 100° C. to about 220° C. 170.A process according to claim 120, 123, 124, 125, 126, 127, 128, 129,130, 131, 132, 133, 134, 135, or 121 wherein the time of polymerizationis from about 2 hours to greater than about 8 hours.
 171. A processaccording to claim 120, 123, 124, 125, 126, 127, 128, 129, 130, 131,132, 133, 134, 135 or 121 wherein said polymerization reaction isconducted at a temperature of from about 100° C. to greater than about185° C.
 172. A fiber spun from said first homo-oligomeric product, saidfirst co-oligomeric product, said first homo-polymeric product, saidfirst copolymeric product, said second homo-oligomeric product, saidsecond co-oligomeric product, said poly-oligomeric product, said firstblock-oligomeric product or said first block-polymeric product of claim169 immediately following polymerization.
 173. A crystalline polymeraccording to claim 2, 40, or 68 in the form of a fiber, film, orfibrids.
 174. A crystalline polymer according to claim 3, 4, 5, 6, 7, 8,9, or 10 in the form of a fiber, film, or fibrids.
 175. A crystallinepolymer according to claim 12, 13, 14, 17, or 18 in the form of a fiber,film, or fibrids.
 176. A crystalline polymer according to claim 2, 3, or4 wherein said polymers I, II, III, IV, V, VI, VII, and VIII arecharacterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 10 dL/g as determined inmethanesulfonic acid at 30° C., with the proviso that when said polymeris poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) thatthe molecular weight of saidpoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity greater than 30.3 dL/g asdetermined in methanesulfonic acid at 30° C.
 177. A crystalline polymeraccording to claim 20 or 21 in the form of a fiber, film, or fibrids.178. A crystalline polymer according to claim 22, 23, or 24 in the formof a fiber, film, or fibrids.
 179. A crystalline polymer according toclaim 25, 26, 27, 28, 29, 30, 31, 32, or 33 in the form of a fiber,film, or fibrids.
 180. A crystalline polymer according to claim 34 inthe form of a fiber, film, or fibrids.
 181. A crystalline polymeraccording to claim 35, 36, or 37 in the form of a fiber, film, orfibrids.
 182. A crystalline polymer according to claim 41, 42, 43, 44,45, 46, 47, or 48 in the form of a fiber, film, or fibrids.
 183. Acrystalline polymer according to claim 49, 50, 51, 52, 53, 54, 55, 56,57, or 58 in the form of a fiber, film, or fibrids.
 184. A crystallinepolymer according to claim 60, 61, 62, 63, 64, or 67 in the form of afiber, film, or fibrids.
 185. A crystalline polymer according to claim5, 6, 7, 8, 9, or 10 wherein said polymer is characterized as having amolecular weight with an n value corresponding to an intrinsic viscositygreater than about 7 dL/g as determined in methanesulfonic acid at 30°C.
 186. A crystalline polymer according to claim 69, 70, 71, 72, 73, 74,75, 76, 77, or 78 in the form of a fiber, film, or fibrids.
 187. Acrystalline polymer according to claim 40 wherein said polymer arecharacterized as having a molecular weight with an n value correspondingto an intrinsic viscosity greater than about 7 dL/g as determined inmethanesulfonic acid at 30° C., with the proviso that when said polymeris IX that the molecular weight of said IX polymer correspond to anintrinsic viscosity greater than 16 dL/g as determined inmethanesulfonic acid at 30° C.
 188. A crystalline polymer according toclaim 68 wherein said polymer are characterized as having a molecularweight with an n value corresponding to an intrinsic viscosity greaterthan about 7 dL/g as determined in methanesulfonic acid at 30° C.
 189. Acrystalline polymer according to claim 79, 80, 81, or 82 in the form ofa fiber, film, or fibrids.
 190. A crystalline polymer according to claim84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, or 97 in the form ofa fiber, film, or fibrids.
 191. A crystalline polymer according to claim99 or 100 in the form of a fiber, film, or fibrids.
 192. A crystallinepolymer according to claim 101, 102, or 103 in the form of a fiber,film, or fibrids.
 193. A crystalline polymer according to claim 106,107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, or 119 inthe form of a fiber, film, or fibrids.
 194. An article comprising acrystalline polymer of claim 2, 40, or 68 in a resinous matrix.
 195. Anarticle comprising a crystalline polymer of claim 3, 4, 5, 6, 7, 8, 9,or 10 in a resinous matrix.
 196. An article comprising a crystallinepolymer of claim 41, 42, 43, 44, 45, 46, 47, or 48, in a resinousmatrix.
 197. An article comprising a crystalline polymer of claim 69,70, 71, 72, 73, 74, 75, 76, 77, or 78 in a resinous matrix.
 198. A fiberdrawn from the liquid crystslline composition of claim 120, 123, 124,125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, or
 121. 199. Afilm extruded from the liquid crystalline composition of claim 120, 123,124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, or
 135. 200. Afiber spun from the liquid crystalline composition of claim 120, 123,124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, or
 135. 201. Acrystalline polymer made by the process of claim 120, 123, 124, 125,126, 127, 128, 129, 130, 131, 132, 133, 134, 135, or
 121. 202. A processaccording to claim 120, 123, 124, 125, 126, 127, 128, 129, 130, 131,132, 133, 134, or 135 further comprising spinning said firsthomo-oligomeric product, said first co-oligomeric product, said firsthomo-polymeric product, said first copolymeric product, said secondhomo-oligomeric product, said second co-oligomeric product, saidpoly-oligomeric product, said first block-oligomeric product or saidfirst block-polymeric product through an air-gap and into a coagulationbath thereby forming a fiber.
 203. A process according to claim 120,123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, or 135further comprising extruding said first homo-oligomeric product, saidfirst co-oligomeric product, said first homopolymeric product, saidfirst copolymeric product, said second homo-oligomeric product, saidsecond co-oligomeric product, said poly-oligomeric product, said firstblock-oligomeric product or said first block-polymeric product into acoagulation bath thereby forming a film.
 204. An article comprising acrystalline polymer of claim 2, 40, or
 68. 205. A process according toclaim 120, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134,or 135 further comprising extruding said first homo-oligomeric product,said first co-oligomeric product, said first homopolymeric product, saidfirst copolymeric product, said second homo-oligomeric product, saidsecond co-oligomeric product, said poly-oligomeric product, said firstblock-oligomeric product or said first block-polymeric product into acoagulation bath thereby forming an article.
 206. A composite filmcomprising a crystalline polymer of claim 2, 40, or
 68. 207. Acrystalline polymer according to claim 2, 40, 68 wherein said polymersare characterized as having a molecular weight with an n valuecorresponding to an intrinsic viscosity greater than about 16 dL/g asdetermined in methanesulfonic acid at 30° C., with the proviso that whensaid polymer ispoly([benzo-(1,2-d:-4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) that themolecular weight of saidpoly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)correspond to an intrinsic viscosity greater than 30.3 dL/g asdetermined in methanesulfonic acid at 30° C.
 208. A composite articlecomprising a resinous matrix reinforced with the crystalline polymer ofclaim 2, 40, or
 68. 209. A fiber according to claim 174 wherein saidfiber is characterized as having a tensile strength greater than 1.37Gpa.
 210. An article comprising a crystalline polymer of claim 2, 3, 4,12, 14, 17, or 18 in admixture with a flexible aromatic heterocyclicpolymer.
 211. A polymer according to claim 136 wherein said polymer is##STR1165##
 212. A polymer according to claim 211 wherein said polymerhas an intrinsic viscosity of from about 15 dL/g to about 42 dL/g. 213.A polymer according to claim 136 wherein said polymer is ##STR1166##214. A polymer according to claim 213 wherein said polymer has anintrinsic viscosity of from about 9 dL/g to about 24 dL/g.
 215. Apolymer according to claim 136 wherein said polymer is ##STR1167## 216.A polymer according to claim 215 wherein said polymer has an intrinsicviscosity of about 15 dL/g.
 217. A polymer according to claim 136wherein said polymer is ##STR1168##
 218. A polymer according to claim217 wherein said polymer has an intrinsic viscosity of about 12 dL/g.219. A polymer according to claim 136 wherein said polymer is##STR1169##
 220. A polymer according to claim 219 wherein said polymerhas an intrinsic viscosity of about 12 dL/g.
 221. A polymer according toclaim 138 wherein said polymer contains the moiety ##STR1170##
 222. Apolymer according to claim 138 wherein said polymer contains the moiety##STR1171##
 223. A polymer according to claim 138 wherein said polymercontains the moiety ##STR1172##
 224. A polymer according to claim 138wherein said polymer contains the moiety ##STR1173##
 225. A polymeraccording to claim 138 wherein said polymer contains the moiety##STR1174##
 226. A polymer according to claim 138 wherein said polymercontains the moiety ##STR1175##
 227. A polymer according to claim 138wherein said polymer contains the moiety ##STR1176##
 228. A polymeraccording to claim 140 wherein said polymer contains the moiety##STR1177##
 229. A polymer according to claim 140 wherein said polymercontains the moiety ##STR1178##
 230. A polymer according to claim 140wherein said polymer contains the moiety ##STR1179##
 231. A polymeraccording to claim 140 wherein said polymer contains the moiety##STR1180##
 232. A polymer according to claim 140 wherein said polymercontains the moiety ##STR1181##
 233. A polymer according to claim 140wherein said polymer contains the moiety ##STR1182##
 234. A polymeraccording to claim 140 wherein said polymer contains the moiety##STR1183##
 235. A process according to claim 202 wherein said spinningis conducted at an initial draw ratio of from about 5:1 to about 50:1.236. A process according to claim 202 wherein said spinning is conductedat a temperature between about 60° C. to about 100° C.
 237. A processaccording to claim 202 wherein said spinning is conducted through anair-gap separation distance of from about 1 cm to about 100 cm beforeallowing said fiber to enter into a coagulation bath.
 238. A polymeraccording to claim 9 wherein said polymer has an intrinsic viscositygreater than about 11 dL/g.
 239. A process according to claim 120, 123,124, 125, 126, 130, or 135 wherein said selected first monomer is3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride.
 240. A processaccording to claim 239 wherein said phosphorus pentoxide content in saidpreliminary solvent is present in an amount below about 77% by weight.241. A process according to claim 239 wherein said phosphorus pentoxidecontent of said first homo-oligomeric product, said first co-oligomericproduct, said first homopolymeric product, said first copolymericproduct, said second homo-oligomeric product, said second co-oligomericproduct, said first block-oligomeric product, or said firstblock-polymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 242. A process according toclaim 120, 123, 124, 125, 126, 130, or 135 wherein said selected firstmonomer is 3,3'-dimercaptobenzidine dihydrochloride.
 243. A processaccording to claim 242 wherein said phosphorus pentoxide content in saidpreliminary solvent is present in an amount below about 77% by weight.244. A process according to claim 242 wherein said phosphorus pentoxidecontent of said first homo-oligomeric product, said first co-oligomericproduct, said first homopolymeric product, said first copolymericproduct, said second homo-oligomeric product, said second co-oligomericproduct, said first block-oligomeric product, or said firstblock-polymeric product formed by said polymerization reaction isbetween about 82% and about 84% by weight.
 245. A fiber spun from thehomo-polymeric product of claim 169 being characterized as having anultimate tensile strength of at least about 2.96 GPa.
 246. A fiber spunfrom the homo-polymeric product of claim 169 being characterized ashaving a modulus of at least about 89.6 GPa.
 247. A fiber spun from thehomo-polymeric product of claim 169 having in combination:a ultimatetensile strength of at least about 2.96 GPa; a modulus of at least about89.6 GPa; and an elongation at break of at least about 4.2 percent. 248.A fiber spun from the homo-polymeric product of claim 169 beingcharacterized as having an ultimate tensile strength of at least about3.45 GPa after heat treatment at about 500° C. in nitrogen for 60seconds.
 249. A fiber spun from the homo-polymeric product of claim 169being characterized as having a modulus of at least about 317 GPa afterheat treatment at about 500° C. in nitrogen for 60 seconds.
 250. A fiberspun from the homo-polymeric product of claim 169 being characterized ashaving in combination:an ultimate tensile strength of at least about3.45 GPa; a modulus of at least about 317 GPa; and an elongation atbreak of at least about 1.8 percent after heat treatment at about 500°C. in nitrogen for 60 seconds.
 251. A fiber spun from the homo-polymericproduct of claim 169 being characterized as having an ultimate tensilestrength of at least about 3.07 GPa after heat treatment at about 450°C. in air for 60 seconds under a stretch factor of about 2 percent. 252.A fiber spun from the homo-polymeric product of claim 169 beingcharacterized as having a modulus of at least about 410 GPa after heattreatment at about 450° C. in air for 60 seconds under a stretch factorof about 2 percent.
 253. A fiber spun from the homo-polymeric product ofclaim 169 being characterized as having in combination:an ultimatetensile strength of at least about 3.07 GPa; and a modulus of at leastabout 410 GPa; after heat treatment at about 450° C. in air for 60seconds under a stretch factor of about 2 percent.
 254. A fiber spunfrom the homo-polymeric product of claim 169 being characterized ashaving an ultimate tensile strength of at least about 3.58 GPa afterheat treatment at about 500° C. in air for 60 seconds under a stretchfactor of about 2.5 percent.
 255. A fiber spun from the homo-polymericproduct of claim 169 being characterized as having a modulus of at leastabout 467 GPa after heat treatment at about 500° C. in air for 60seconds under a stretch factor of about 2.5 percent.
 256. A fiber spunfrom the homo-polymeric product of claim 169 being characterized ashaving in combination:an ultimate tensile strength of at least about3.58 GPa; and a modulus of at least about 467 GPa; after heat treatmentat about 500° C. in air for 60 seconds under a stretch factor of about2.5 percent.
 257. A fiber spun from the homo-polymeric product of claim169 being characterized as having an ultimate tensile strength of atleast about 3.07 GPa after heat treatment at about 450° C. in air for 60seconds under a stretch factor of about 2.8 percent.
 258. A fiber spunfrom the homo-polymeric product of claim 169 being characterized ashaving a modulus of at least about 394 GPa after heat treatment at about450° C. in air for 60 seconds under a stretch factor of about 2.8percent.
 259. A fiber spun from the homo-polymeric product of claim 169being characterized as having in combination:an ultimate tensilestrength of at least about 3.07 GPa; and a modulus of at least about 394GPa; after heat treatment at about 450° C. in air for 60 seconds under astretch factor of about 2.8 percent.
 260. A process according to claim127 wheren the time of polymerization is from about 1 hour to about 3hours.
 261. A fiber spun from the composition of claim 200 having aultimate tensile strength of at least about 2.34 GPa.
 262. A fiber spunfrom the composition of claim 200 having a ultimate tensile strength ofat least about 3.57 GPa.
 263. A fiber spun from the composition of claim200 having a ultimate tensile strength of at least about 2.57 GPa. 264.A fiber spun from the composition of claim 200 having a ultimate tensilestrength of at least about 2.83 GPa.
 265. A fiber spun from thecomposition of claim 200 having a ultimate tensile strength of at leastabout 2.76 GPa.
 266. A fiber spun from the composition of claim 200having a ultimate tensile strength of at least about 5.01 GPa.
 267. Afiber spun from the composition of claim 200 having a ultimate tensilestrength of at least about 3.38 GPa.
 268. A fiber spun from thecomposition of claim 200 having a ultimate tensile strength of at leastabout 3.29 GPa.
 269. A fiber spun from the composition of claim 200having in combination:an ultimate tensile strength of at least about2.34 GPa; and a modulus of at least about 41 GPa.
 270. A fiber spun fromthe composition of claim 200 having in combination:an ultimate tensilestrength of at least about 2.76 GPa; and a modulus of at least about 41GPa.
 271. A fiber spun from the composition of claim 200 having incombination:an ultimate tensile strength of at least about 3.57 GPa; amodulus of at least about 133 GPa; and an elongation at break of atleast about 3.3 percent.
 272. A fiber spun from the composition of claim200 having in combination:an ultimate tensile strength of at least about2.57 GPa; a modulus of at least about 79 GPa; and an elongation at breakof at least about 4.6 percent.
 273. A fiber spun from the composition ofclaim 200 having in combination:an ultimate tensile strength of at leastabout 2.83 GPa; a modulus of at least about 61 GPa; and an elongation atbreak of at least about 4.8 percent.
 274. A fiber spun from thecomposition of claim 200 having a ultimate tensile strength of at leastabout 4.94 GPa after heat treatment at about 450° C. in nitrogen for 30seconds under a stretch factor of about 4.37 percent.
 275. A fiber spunfrom the composition of claim 200 having a ultimate tensile strength ofat least about 3.34 GPa after heat treatment at about 400° C. innitrogen for 30 seconds under a stretch factor of about 4.37 percent.276. A fiber spun from the composition of claim 200 having a ultimatetensile strength of at least about 2.62 GPa after heat treatment ofabout 500° C. in nitrogen for 30 seconds under a stretch factor of about1.28 percent.
 277. A fiber of the polymer of claim 213 beingcharacterized as having an ultimate tensile strength of at least about2.96 GPa.
 278. A fiber of the polymer of claim 213 being characterizedas having a modulus of at least about 89.6 GPa.
 279. A fiber of thepolymer of claim 213 having in combination:a ultimate tensile strengthof at least about 2.96 GPa; a modulus of at least about 89.6 GPa; and anelongation at break of at least about 4.2 percent.
 280. A fiber of thepolymer of claim 213 being characterized as having an ultimate tensilestrength of at least about 3.45 GPa after heat treatment at about 500°C. in nitrogen for 60 seconds.
 281. A fiber of the polymer of claim 213being characterized as having a modulus of at least about 317 GPa afterheat treatment at about 500° C. in nitrogen for 60 seconds.
 282. A fiberof the polymer of claim 213 being characterized as having incombination:an ultimate tensile strength of at least about 3.45 GPA; amodulus of at least about 317 GPa; and an elongation at break of atleast about 1.8 percent after heat treatment at about 500° C. innitrogen for 60 seconds.
 283. A fiber of the polymer of claim 213 beingcharacterized as having an ultimate tensile strength of at least about3.07 GPa after heat treatment at about 450° C. in air for 60 secondsunder a stretch factor of about 2 percent.
 284. A fiber of the polymerof claim 213 being characterized as having a modulus of at least about410 GPa after heat treatment at about 450° C. in air for 60 secondsunder a stretch factor of about 2 percent.
 285. A fiber of the polymerof claim 213 being characterized as having in combination:an ultimatetensile strength of at least about 3.07 GPa; and a modulus of at leastabout 410 GPa; after heat treatment at about 450° C. in air for 60seconds under a stretch factor of about 2 percent.
 286. A fiber of thepolymer of clain 213 being characterized as having an ultimate tensilestrength of at least about 3.58 GPa after heat treatment at about 500°C. in air for 60 seconds under a stretch factor of about 2.5 percent.287. A fiber of the polymer of claim 213 being characterized as having amodulus of at least about 467 GPA after heat treatment at about 500° C.in air for 60 seconds under a stretch factor of about 2.5 percent. 288.A fiber of the polymer of claim 213 being characterized as having incombination:an ultimate tensile strength of at least about 3.58 GPa; anda modulus of at least about 467 GPa; after heat treatment at about 500°C. in air for 60 seconds under a stretch factor of about 2.5 percent.289. A fiber of the polymer of claim 213 being characterized as havingan ultimate tensile strength of at least about 3.07 GPa after heattreatment at about 450° C. in air for 60 seconds under a stretch factorof about 2.8 percent.
 290. A fiber of the polymer of claim 213 beingcharacterized as having a modulus of at least about 394 GPa after heattreatment at about 450° C. in air for 60 seconds under a stretch factorof about 2.8 percent.
 291. A fiber of the polymer of claim 213 beingcharacterized as having in combination:an ultimate tensile strength ofat least about 3.07 GPa; and a modulus of at least about 394 GPa; afterheat treatment at about 450° C. in air for 60 seconds under a stretchfactor of about 2.8 percent.
 292. A fiber of the polymer of claim 219having in combination:an ultimate tensile strength of at least about2.34 GPa; and a modulus of at least about 136 GPa; after heat treatmentat about 500° C. in nitrogen for 60 seconds under a stretch factor ofabout 7.5 percent.
 293. A fiber of the polymer of claim 219 having incombination:an ultimate tensile strength of at least about 2.85 GPa; amodulus of at least about 119 GPa; and an elongation at break of atleast about 2.5 percent after heat treatment at about 500° C. innitrogen for 30 seconds under a stretch factor of about 4.37 percent.294. A fiber of the polymer of claim 219 having in combination:anultimate tensile strength of at least about 3.34 GPa; a modulus of atleast about 115 GPa; and an elongation at break of at least about 3.6percent after heat treatment at about 400° C. in nitrogen for 30 secondsunder a stretch factor of about 4.37 percent.
 295. A fiber of thepolymer of claim 219 having in combination:an ultimate tensile strengthof at least about 2.62 GPa; a modulus of at least about 144 GPa; and anelongation at break of at least about 2.2 percent after heat treatmentat about 500° C. in nitrogen for 30 seconds under a stretch factor ofabout 1.28 percent.
 296. A fiber of the polymer of claim 219 having aultimate tensile strength of at least about 2.34 GPa.
 297. A fiber ofthe polymer of claim 219 having a ultimate tensile strength of at leastabout 3.57 GPa.
 298. A fiber of the polymer of claim 219 having aultimate tensile strength of at least about 2.57 GPa.
 299. A fiber ofthe polymer of claim 219 having a ultimate tensile strength of at leastabout 2.83 GPa.
 300. A fiber of the polymer of claim 219 having aultimate tensile strength of at least about 2.76 GPa.
 301. A fiber ofthe polymer of claim 219 having a ultimate tensile strength of at leastabout 5.01 GPa.
 302. A fiber of the polymer of claim 219 having aultimate tensile strength of at least about 3.38 GPa.
 303. A fiber ofthe polymer of claim 219 having a ultimate tensile strength of at leastabout 3.29 GPa.
 304. A fiber of the polymer of claim 219 having incombination:an ultimate tensile strength of at least about 2.34 GPa; anda modulus of at least about 41 GPa.
 305. A fiber of the polymer of claim219 having in combination:an ultimate tensile strength of at least about2.76 GPa; and a modulus of at least about 41 GPa.
 306. A fiber of thepolymer of claim 219 having in combination:an ultimate tensile strengthof at least about 3.57 GPa; a modulus of at least about 133 GPa; and anelongation at break of at least about 3.3 percent.
 307. A fiber of thepolymer of claim 219 having in combination:an ultimate tensile strengthof at least about 2.57 GPa; a modulus of at least about 79 GPa; and anelongation at break of at least about 4.6 percent.
 308. A fiber of thepolymer of claim 219 having in combination:an ultimate tensile strengthof at least about 2.83 GPa; a modulus of at least about 61 GPa; and anelongation at break of at least about 4.8 percent.
 309. A fiber of fromthe polymer of claims 219 having an ultimate tensile strength of atleast about 4.94 GPa after heat treatment at about 450° C. in nitrogenfor 30 seconds under a stretch factor of about 4.37 percent.
 310. Afiber of the polymer of claim 219 having a ultimate tensile strength ofat least about 3.76 GPa after heat treatment at about 400° C. innitrogen for 30 seconds under a stretch factor of about 4.37 percent.311. A fiber of the polymer of claim 219 having a ultimate tensilestrength of at least about 3.00 GPa after heat treatment at about 500°C. in nitrogen for 30 seconds under a stretch factor of about 1.28percent.
 312. A process according to claim 120, 123, 126, or 127 whereinsaid steps are conducted within the shaded phosphorus pentoxide contentprofile area bounded by ABCDEFGHI of FIG.
 14. 313. A process accordingto claim 120, 124, 128, 129, or 130 wherein said steps are conductedwithin the shaded phosphorus pentoxide content profile area bounded byABCDEFGHI of FIG.
 14. 314. A process according to claim 120, 125, 131,132, 133, 134, or 135 wherein said steps are conducted within the shadedphosphorus pentoxide content profile area bounded by ABCDEFGHI of FIG.14.
 315. A process according to claim 120, 127, 128, 129, 132, 133, 134,or 135 wherein said steps are conducted within the shaded phosphoruspentoxide content profile area bounded by ABCDEFGHI of FIG.
 14. 316. Aprocess according to claim 120, 123, 124, 125, 126, 127, 128, 129, 130,131, 132, 133, 134, or 135 wherein said steps are conducted within theshaded phosphorus pentoxide content profile area bounded by ABCDEFGHI ofFIG.
 14. 317. A process according to claim 121 wherein said reactionmedium of step (a) is prepared in polyphosphoric acid having aphosphorus pentoxide content range of from about 62% to about 84%. 318.A process for preparing a liquid crystalline extended chain polymercomposition of workable viscosity which is useful in the production offibers and films comprising the following steps:(a) preparing a reactionmedium suitable for polymerization, said reaction medium being preparedby incorporating a high concentration of at least one of a selectedmonomer in a polyphosphoric acid having a relatively low phosphoruspentoxide content; (b) conducting polymerization of said monomersubstantially within the shaded phosphorus pentoxide content profilearea bounded by DCGFE of FIG.
 14. 319. A process according to claim 316further comprising spinning said first homo-oligomeric product, saidfirst co-oligomeric product, said first homo-polymeric product, saidfirst copolymeric product, said second homo-oligomeric product, saidsecond co-oligomeric product, said poly-oligomeric product, said firstblock-oligomeric product or said first block-polymeric product throughan air-gap and into a coagulation bath thereby forming a fiber.
 320. Aprocess according to claim 316 further comprising extruding said firsthomo-oligomeric product, said first co-oligomeric product, said firsthomopolymeric product, said first copolymeric product, said secondhomo-oligomeric product, said second co-oligomeric product, saidpoly-oligomeric product, said first block-oligomeric product or saidfirst block-polymeric product through an air-gap and into a coagulationbath thereby forming a film.
 321. A process according to claim 122,wherein m_(o) is present in an amount below about 77% by weight.
 322. Acrystalline polymer according to claim 2 or 5 wherein said polymer is aformula II extended chain homopolymer having the formula: ##STR1184##wherein said polymer is characterized as having a molecular weight withan n value corresponding to an intrinsic viscosity greater than about 5dL/g as determined in methanesulfonic acid at 30° C.
 323. A crystallinepolymer according to claim 322 wherein said polymer is characterized ashaving a molecular weight with an n value corresponding to an intrinsicviscosity of at least about 7 dL/g as determined in methanesulfonic acidat 30° C.
 324. A crystalline polymer according to claim 322 in the formof a fiber, said fiber being characterized as having a tensile strengthgreater than 1.37 GpA.
 325. A crystalline polymer according to claim 2or 4 wherein said polymer is a formula I extended chain homopolymerhaving the formula: ##STR1185## wherein n is greater than
 60. 326. Acrystalline polymer according to claim 2 or 4 wherein said polymer is aformula I extended chain crystalline homopolymer having the formula:##STR1186## wherein n is greater than
 60. 327. A crystalline polymeraccording to claim 2, 40, or 68 wherein said organic group is phenyl,pyridyl, or methyl.
 328. An article comprising the crystalline polymerof claim 2, 3, or 4 in admixture with a flexible aromatic heterocyclicpolymer.
 329. An article comprising the crystalline polymer of claim 3,4, 5, 6, 7, 8, 9,
 10. 330. An article comprising the crystalline polymerof claim 12, 13, 14, 17, or
 18. 331. An article comprising thecrystalline polymer of claim 20 or
 21. 332. An article comprising thecrystalline polymer of claim
 24. 333. An article comprising thecrystalline polymer of claim 22, 23, 25, 26, 27, 28, 29, 30, 31, 32, or33.
 334. An article comprising the crystalline polymer of claim
 34. 335.An article comprising the crystalline polymer of claim 41, 42, 43, 44,45, 46, 47, or
 48. 336. An article comprising the crystalline polymer ofclaim 69, 70, 71, 72, 73, 74, 75, 76, 77, or
 78. 337. A compositearticle comprising a resinous matrix reinforced with the crystallinepolymer of claim 3, 4, 5, 6, 7, 8, 9, or
 10. 338. A composite articlecomprising a resinous matrix reinforced with the crystalline polymer ofclaim 41, 42, 43, 44, 45, 46, 47, or
 48. 339. A composite articlecomprising a resinous matrix reinforced with the crystalline polymer ofclaim 69, 70, 71, 72, 73, 74, 75, 76, 77, or
 78. 340. A processaccording to claim 121 further comprising spinning said liquidcrystalline extended chain polymer composition through an air-gap andinto a coagulation bath thereby forming a fiber.
 341. A processaccording to claim 121 further comprising extruding said liquidcrystalline extended chain polymer composition through an air-gap andinto a coagulation bath thereby forming a film.
 342. An articlecomprising the crystalline polymer of claim
 1. 343. A composite articlecomprising a resinous matrix reinforced with the crystalline polymer ofclaim
 1. 344. A crystalline polymer according to claim 1 in the form ofa fiber, film, or fibrids.
 345. An article comprising a crystallinepolymer of claim 1 in admixture with a flexible aromatic heterocyclicpolymer.
 346. An article comprising an admixture of two or more polymersof claim 1.